Okay, first off, welcome to the boards. 
Now onto my thoughts. If you're planning on using your attacks often, I would recommend picking up Stamina, they will eat away at your endurance. But if you're mostly teaming, you'll be healing/buffing alot of the time.
Absorb pain is actually a very nice power, but some people will disagree. I personally didn't take it on my Empath while I was leveling, I only respeced into it at level 50, but now I'd never be without it.
As for the epic, Power Mastery is definately a good choice, but not the only one. It's main selling point is really Power Build Up, which improves your heals and (some) of your buffs quite a bit, but only for a short time. Conserve power is also very useful if you're running a stamina-less build.
Psi is pretty nice, but I will warn you that the AoE sleep won't be much use if you're teaming with your wife most of the time. Fire is heavy on the AoE's, so they enemies won't stay asleep for long. The hold is nice, and Telekinesis is pretty handy, but the massive end drain means you won't be able to use it all that often without stamina.
I can't comment too much on the Psi secondary, I've never used it myself, but I'm sure someone that has will be along soon enough.
Welcome indeed
So some musings
First one I really would take Stamina its pretty much a must have once you start using a lot of powers. You can survive without it but I'd really take it.
Absorb Pain is a power of some debate, like Empath I got to 50 on my own emp without using it and am of the opinion that its at its best in PvP which you say you are not interested in so its skippable, still it is a spare heal and a good one.
Psi: Hmm far from an expert but take Subdue its good damage and an immobalise and will be useful if you are planning to be more aggresive. Also take Will Domination as its a solid damage single target mez. I would advise against AoE sleeps unless you have a team that is used to them/prepared to learn to work with them as they quickly get turned off with AoEs.
Power Pools: I would agree you should consider taking recall friend for rezzing I did and it was handy.
Travel Power: Your not PvPing so take whatever you think is cool imo
Epic Pools: Short answer Power Mastery really is great and having had both Power Mastery and Psi Mastery on White Magus I would prefer Power, but its not an absolute must just handy.
So heres a rough and quick build, be warned I am no expert at all on /Psi so its all best guess on that one. Also since you said you wanted to be soloable I have taken a good few attacks. Fitting Hasten from the Speed pool in could be good imo but went with attacks instead to give you flexability.
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Exported from Ver: 1.7.6.0 of the CoH_CoV Character Builder - (http://sherksilver.coldfront.net/index.php)
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Name:
Level: 50
Archetype: Defender
Primary: Empathy
Secondary: Psychic Blast
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01) --> Healing Aura==> Rechg(1) Rechg(3) Rechg(3) Heal(5) Heal(5) Heal(7)
01) --> Mental Blast==> Acc(1) Dmg(25) Dmg(50)
02) --> Heal Other==> Rechg(2) Rechg(7) Rechg(9) Heal(9) Heal(11) Heal(11)
04) --> Subdue==> Acc(4) Dmg(25) Dmg(27) Dmg(46)
06) --> Resurrect==> Rechg(6)
08) --> Clear Mind==> Rechg(8)
10) --> Hover==> Fly(10) Fly(23)
12) --> Fortitude==> Rechg(12) Rechg(13) Rechg(13) DefBuf(15) DefBuf(15) DefBuf(17)
14) --> Fly==> EndRdx(14) Fly(17) Fly(19)
16) --> Swift==> Fly(16) Fly(19) Fly(21)
18) --> Hurdle==> Jump(18)
20) --> Stamina==> EndMod(20) EndMod(21) EndMod(23)
22) --> Will Domination==> Acc(22) Sleep(34) Sleep(34) Rechg(50)
24) --> Recovery Aura==> Rechg(24) Rechg(29) Rechg(29) EndMod(31) EndMod(33) EndMod(33)
26) --> Regeneration Aura==> Rechg(26) Rechg(27) Rechg(31) Heal(31) Heal(33) Heal(34)
28) --> Recall Friend==> Range(28)
30) --> Absorb Pain==> Rechg(30) Rechg(36) Heal(36) Heal(36) Heal(37)
32) --> Adrenalin Boost==> Rechg(32) Rechg(37) Rechg(37) EndMod(39) EndMod(39) Heal(39)
35) --> Telekinetic Blast==> Acc(35) Dmg(40) Dmg(42) Dmg(42)
38) --> Psychic Wail==> Acc(38) Dmg(40) Dmg(40) Dmg(42)
41) --> Power Build Up==> Rechg(41) Rechg(43) Rechg(43) TH_Buf(43) TH_Buf(45) TH_Buf(45)
44) --> Temp Invulnerability==> EndRdx(44) DmgRes(45) DmgRes(46) DmgRes(46)
47) --> Total Focus==> Acc(47) Dmg(48) Dmg(48) Dmg(48) Rechg(50)
49) --> Conserve Power==> Rechg(49)
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01) --> Sprint==> Empty(1)
01) --> Brawl==> Empty(1)
01) --> Vigilance==> Empty(1)
02) --> Rest==> Empty(2)
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Hope that helps and enjoy yourself
Cheers,
White 
Absorb pain, properly slotted, can bring a tank from red to full HP. An empath should never be without it.
As for Psi, your main attack chain will propably be Subdue, TK blast and will dom, with maybe some AoE's thrown in.
My initial suggestion would be to not plan for level 41+ just yet, unless you're expecting to hit 35 this week. You will learn more about your character in the comming levels and there are some changes in opponents that can alter your perception of useful powers.
WMs build is fairly solid, but I would rearrange some powers and slots. One choice would be delaying Resurrect to get Recovery Aura at 18 for exemplaring purposes (a res is never as good as a power that keeps the team fighting/out of debt). Also, To-Hit buffs in PBU is a pure PvP choice, it's fairly pointless to do so for PvE purposes.
The first thing I think you should do is install the test client and copy your character to the Training Room (you can find instructions on how to do both in the Training Room forum) a couple of times and convince your wife to do the same. Then you play around with a few different respecs. You will need to copy your character as many times as you need respecs and you need to do it before you spend it on your live character. That way you get to check out how things work for you before you lock in your live character for ~10 levels.
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Absorb pain, properly slotted, can bring a tank from red to full HP. An empath should never be without it.
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Guess we'll have to agree to disagree.
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WMs build is fairly solid, but I would rearrange some powers and slots. One choice would be delaying Resurrect to get Recovery Aura at 18 for exemplaring purposes (a res is never as good as a power that keeps the team fighting/out of debt). Also, To-Hit buffs in PBU is a pure PvP choice, it's fairly pointless to do so for PvE purposes.
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Theres very much a playstyle choice element to when you take powers and these are valid points. Also yup I did slot PBU for PvP dont need to do the tohit buffs in PvE maybe one but certainly not three, my bad
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The first thing I think you should do is install the test client and copy your character to the Training Room (you can find instructions on how to do both in the Training Room forum) a couple of times and convince your wife to do the same. Then you play around with a few different respecs. You will need to copy your character as many times as you need respecs and you need to do it before you spend it on your live character. That way you get to check out how things work for you before you lock in your live character for ~10 levels.
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Agreed, test server is your friend here
Cheers,
White
Although it's harder to test an Empathy build on Test. You really need a team to test it properly.
I have a level 29 Emp/Psi Def.
Something to consider, when choosing your travel power is the amount of KB, Holds, Mez, sleeps etc that will be coming your way later in the game.
CJ and Acro are your friends here - particularly if you are going to attack a lot as well.
Hover will help with KB but if you go with hover/fly only you better take a few BF's to each mission that has enemies that have these effects.
As far as stamina is concerned... If you intend to attack as much as you can then I would take certainly take it. If you just want to heal/buff then don't.
As far as Absorb Pain is concerned, it's a very situational power and one that I respecced out. I will probably respec it back in when I get to around lev 40.
As Max stated it can make a huge difference to even a Tank's massive HP's. Very useful when you start to meet AV's on a regular basis.
Proud member of FOXBASE ALPHA and coalition associates.
Hero 50's - 25
Villain 50's - 1
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Absorb pain, properly slotted, can bring a tank from red to full HP. An empath should never be without it.
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Agreed though I really miss its pre ED days. 
Worth noting here is that while AP stops you from healing yourself via instant healing powers healing over time, ie. Regen Aura, does still heal you.
I have regen aura in my build solely for this reason.
Defiant
Proud Member of the Liberty Legion
Venture - Emp/En Defender
Seph - Kat/SR Scrapper
Blizzard - Ice/Storm Controller
Legionelosis - Rad/Rad Defender
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Absorb pain, properly slotted, can bring a tank from red to full HP. An empath should never be without it.
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Agreed though I really miss its pre ED days.
Worth noting here is that while AP stops you from healing yourself via instant healing powers healing over time, ie. Regen Aura, does still heal you.
I have regen aura in my build solely for this reason.
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Why solely for that reason? Regen Aura is an amazing power!
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Absorb pain, properly slotted, can bring a tank from red to full HP. An empath should never be without it.
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Disagree, sry ... Once you get to SOs (Yes, AP will be useful before then) the heal aura and heal other power 6 slotted with 3 recharge enhants will recharge quickly enough.
Not against Absorb Pain, but it's not a must.
ye i take other powers than AP, heal aura + heal other slotted as 3heal/2recharge/1endrdx = fast reloads and never a need for AP really, also stops the chance of u dying faster than a giant kill0r wabbit stomping on teh people in a city
On my EMp/NRG's trip to 50, although this was Pre ED, I never even took AP. It's a very volatile subject, talking about it. IMO, now that ED's here, it's not a must have, but can be useful.
Defiant 50's
Many and varied!
@Miss Chief
I'm now a level 25 Empath/Psionic Blast defender, and I've just done the respec TF and I am looking to streamline my build a little, but before I make a mistake, I'd like to ask the more experienced players for a little guidance, as this is my first toon in CoX and I've only been here a couple of weeks.
Although I will rarely need to solo (as I play CoH with my Fire/Fire Blaster Wife too, on top of mainly grouping), I still want a balanced Psi/Empath build. I'm not a PvPer either.
Looking at the Empath skill list, the only skill I'm NOT looking at is Absorb Pain. The rest seem pretty useful for team play.
On the Psi list, I'm a little more unsure. Probaly NOT Subdue, Psychic Scream, & Scramble Thoughts, but most of the rest.
Extra pools, I was currently looking at:
Hover, Fly (as main transport to & in missions)
Recall Friend (for ressing)
After that, I'm not sure...
Some people seem to like Fitness pool for Stamina, however so far I do not run out of Endurance in groups...
Leadership seems good for buffs, but only if people are in range...
Other pools... I don't know.
And looking ahead... Is Power Mastery 'really' that great? At first glance to me it doesn't seem 'that' good, and I think that Psychic Mastery may be preferable.
I've played with a few different types of builds in planners, but can't really decide what would actually be better when playing.
I know I can change again in another 10 levels, but I'd like to try and get on a good path.
I've seen quite a few 'guides', but many seem out of date, so has anyone got any comments on my first impressions, or have some good insights for me?
Thanks