If you're planning on using your Adcom to do the DAC step then the analogue-out quality of whatever sound-card you get is pretty much irrelevant because you won't be using it. Digital out is pretty much digital out. Either it works or it doesn't. I'm sure there are some Jitter-bugs reading this, but even they will have to admit that the differences between digital outs on high and low end cards will be highly subtle, if they exist at all!
The only thing you *might* notice is whether or not the soundcard resamples before out-putting through the S/PDIF. The Audigy2 resamples everything to a multiple of 48Khz. and there isn't much you can do about it. M-Audio and RME cards as well as a few others can output 44.1 Khz as well as a slough of other sampling rates, which means you can get bit-perfect digital pass-through. (i.e. Exactly the same bits that would come out of a CD transport) This is the way to go if you have great ears/gear or are just anal retentive.
You do need to do a couple things to get bit-perfect output though. First of all, if you're using Windows you need to use a plug-in for Winamp (or whatever player you use) that supports kernel streaming or ASIO output. If you just use the default wave-out/directsound renderer everything will go through Windows kmixer which will happily mulch everything into 48Khz regardless of how expensive your soundcard is. A great test to see if you have bit-perfect output is to try playing a DTS CD (Ech. Yes, I know they suck) on your Computer with a DTS capable decoder on the other end of the line. If you get static, resampling is occurring.
Anything you play on your machine will be converted to a PCM stream and sent over the S/PDIF, so you will be able to play Mp3's over S/PDIF on your adcom. It just has to decode PCM, or Dolby/DTS if you're playing a movie. However, as others have suggested, it may be time to go lossless. You're worrying about a lot of stuff that makes far less difference than going from lossy to lossless codecs.
The nice thing about lossless formats is that you can always convert back to the original wav's without losing a single bit of real data. If you decide to switch formats in the future, no worries! Pick one and go crazy. I actually have a mixture of both APE and FLAC files on my machine. You can use both formats simultaneously without any problems. If they don't sound *exactly* the same then either you're imagining it or there is something seriously wrong. Both formats are converted back to the original wav's "on the fly" when they are played. If you code one wav into two different lossless formats and then decode them back again and get two different wav's something is seriously wrong! The conversion between wav and a lossless format *has* to be both one-to-one and onto by definition, or it's not lossless. The only practical difference between lossless formats is the compression ratio's they achieve.
As for selecting between head-phone or speakers... If you're hooking the cans into your Adcom and your speakers as well then the switching is up the the Adcom. If you're going to hook the speakers up to the soundcard (with an amp in between?) and the cans to the Adcom, then it will depend on whatever card you get. For example, the M-Audio Revolution lets you switch in between digital-out and a head-phone jack but you would have to manually switch between the two. (The Revo has separate jacks for phones and speakers) It would not be automatic. I can't speak for any other cards.