Hi,
I have problems with voice chat in Steam and TF2 too. If I go into settings and into the Voice tab, I get "no recording device detected", even though when I click "Test Microphone", everything works. That could be related to the main problem - in TF2, no matter whether I select "Press to talk" or "Automatically transfer my voice whenever I speak", my voice is not transmitted, even though the microphone tests out fine in-game.
Thanks!