It's because the majority of PC games do not use DTS or Dolby 5.1, like DVD's and Blu-ray's do. Some games do though, I think Battlefield games do.
When watching a DVD on a PC connected to a home theatre system, the Dolby or DTS 5.1 track will be passed on by the software media player to the external home theatre system to decode. As games do not have Dolby/DTS tracks, you only get stereo.
SPDIF (optical/coaxial) was designed to be stereo. Only later did companies think of using SPDIF for 5.1 and surround sound purposes. Dolby Digital and DTS were created in order for 5.1 sound to be compressed, so that it can be sent over optical or coaxial.
So unless the sound is encoded with either Dolby or DTS, you will only get stereo.
What you need is Dolby Digital Live, or DTS Connect. Both are real time 5.1 encoders, that take any sound and encode it so it can be passed on to an external system, to be decoded.
Some motherboards come with these features, although they tend to be the higher end boards. Majority of boards do not have these features though, so a sound card is needed that can encode to Dolby or DTS 5.1 in real time.
Cheapest card that can do this, is the Xonar DS. It can only do DTS though, not Dolby. Cheapest card that can encode to Dolby, is the Xonar D1/DX. That can't do DTS, only Dolby.