I guess your headphone amplifier has just analogue inputs so don't even try that, you could just waste your headphones with no chance for it to work!
It seems the panel has sh*tload of inputs but no reasonable analogue output.
QUOTE
Line level out (Front / Rear / Center / Subwoofer / Rear Center) via 3.50mm mini jacks
The soundcard seems to have plain line-out, you could try to plug the headphone amplifier into Front line-out (probably at the rear panel of the soundcard). Just have your PC volume lowered before trying out and make sure you have SPDIF disabled just in case (I managed to drive the digital output to my headphones with Live 5.1 once and I almost wasted both my ears and my headphones).
EDIT: Now it seems that the Front line-out is already amplified, so you could try connecting the amplifier to Rear out and somehow persuade the player to use these two (unamplified) channels instead. This is quite easy with media player classic and a matrix mixer, you might not be able to achieve this with a music player, though.
Note that by driving the signal through the X-Fi's amplifier, you may be sacrificing the deepest bass. Some people reported that X-Fi is somewhat lacking in this department.