your samsung 5.1, is it a HTIB (home theater in a box) type unit? ive heard of issues with some of these where they are not providing surround sound via auxilliary (ie, anything but the included dvd player) inputs and only provide stereo. look in your manual to see if there are any such limitations listed. it could very well be the PCM issue with optical listed above but i think hdmi inputs were tried as well if i remember.
i personally have my receiver (not from a htib set) connected up to my pc via a dvi-to-hdmi cable and i get perfect 5.1 sound. from the pc it is either stereo (while in windows), DD (while playing movies) or i believe PCM (while playing games). I have a ps3 hooked up and it plays via PCM on a hdmi input as well.
you can see the receiver, pc, ps3 and some speakers here...
this is the type of cable i use...
in my windows settings my receiver (in this case vsx-30) is displayed as the primary audio device.
this is what the windows 7 sound devices looks like...
a direct hdmi cable (instead of dvi-to-hdmi like i did because my gtx470 doesnt have hdmi) should work similarly.
i know spdif will support 5.1 speakers (after all the logitech z5500 5.1 uses spdif in) but as mentioned earlier this might be for normal DD and not newer formats. i also know that people can and do use spdif optical to get 5.1 sound out of receivers.
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try hdmi input but it sounds like it may be an issue with your receiver if you have a htib set.
also make sure that you are playing a 5.1 audio source such as a dvd or game. windows will be stereo only!
let us know the results.