While it -did- work for a short period of time(it was right after I updated Edgy to Dapper and the headphones sound stopped working when I rebooted), it's not quite doing so right now, else I wouldn't be asking.

As far as I can tell, alsamixer or KMix is being dumb. I managed to point them towards the device(it was working with the ATI device the first time around, but it was trying to run the Realtek one that didn't have many options at all, let alone any that would solve my problem) that it should be using; strangely enough, an option that was there when sound -was- working(Surround, I believe) is gone and the Headphone Jack Sense button in KMix has no volume control underneath it.

Sometimes my Alsa forgets what it supposed to be doing and I lose all sound. Fix it with the command console.
and set everything to just below Red, unmuting with 'm' as required.

Sometimes headphones are oddly named as wave_centre or similar.
as root stores it for future.