In your case it's possible in two ways:
1. The better one:
Using a filter such as ffdshow to decode mp3s only (rather than AC3, DTS) and direct its output to the analog output (i.e. headphones).
In this case it's possible to use just one software such as Vista MCE using a ffdshow plug-in: http://damienbt.free.fr/.
Just follow the instructions on the above site but:
When installing ffdshow you must specify it to decode only the codecs (types of sound files) that you want on the digital output (such as AC3, DTS and other codecs used in movies). Be aware not to choose mp3 for example (you want it on the headphones).
After installing everything, go to ffdshow audio configuration and change the output device to the soundcard's digital output device.
Choose the windows primary sound device as the headphones.
2. Using two applications (Winamp, Vlc, Foobar, vista MCE, windows media player), each directing its output to different card output (i.e. digital, analog, headphones etc).