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Yep, just connect the headphone amplifier to the "line 1" jack on the sound card and in the control panel set output to "2 Speaker".
This will give you 2.0 stereo output to the headphones amplifier.
Actually, you don't want to do that, because newer games using XAudio2, FMOD, and so forth look at the Windows sound control panel setting. If it only sees stereo, stereo is all the imaging you get when using CMSS-3D Headphone (which only becomes available when the X-Fi control panel is set to Headphones, and yes, they can be set asynchronously). Don't worry about not being able to hear anything; the X-Fi will downmix automatically, whether CMSS-3D Headphone is on or off.
DirectSound3D and OpenAL games don't have this problem since they have a proper sound renderer that gives 3D spatial coordinates for the sound driver to work with (it's not the API/audio renderer's job to decide where and how to play back those sounds, but the sound card driver's job), and CMSS-3D Headphone can just work off that directly instead of having to map everything to a virtual 7.1 speaker configuration first.
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Well, going a bit towards the road of off topic now, but while we are talking about it, both Asus Xonar Essence STX and Creative X-Fi Titanium HD looks interesting, but am leaning towards Asus as i want to try out something new. But are there any major differences between the two? Don't really care that much for EAX, don't think a lot of games use it these days anyway? But yea my computer is used for gaming, but i listen to a lot of music as well.
I still play a lot of older games, so EAX has quite a bit of importance to me. Don't know about your tastes in games, though. If it's some newer title that's downgraded its audio with XAudio2 or FMOD or some such audio renderer that pre-mixes the sounds to surround speaker positions before it ever hits the sound card driver, then it mostly becomes a matter of which card's sound signature you prefer and whether you favor CMSS-3D Headphone or Dolby Headphone as your binaural surround filter of choice (if you even choose to use either; some people don't like either one at all and just play in stereo).
Anyway, as for connecting an amp, you may need a 3.5mm TRS to dual RCA adapter (or a straight-up cable built like that, like what you can get on Monoprice), since most amps have dual RCA inputs. This gives you more flexibility in sound cards, though you'll still be limited to XtremeMusic sound quality. It's your call as to which route you want to take, partially decided by what headphones you're trying to amp to begin with.