Michael V
100+ Head-Fier
No. Any difference there would be between optical and USB would be much, much, much smaller than the difference between using your internal soundcard and using an external DAC and a tube hybrid amp. If you can't hear a difference between these two setups with optical, you won't hear it with USB.
(And it's totally reasonable not to hear a difference, if your computer was providing enough power to drive those headphones well at the level you listen to.)
The Xonar is pretty good as far as sound cards go.
Just give your brain and ears time to develop. There will be very slight differences that you will begin to perceive. Have one reference track that you know inside and out. Listen to the small details. The etching in the track. The high pitch from a triangle. Or the rub of fingers on a guitar string. The decay of a piano note. Focus on them. Listen to it again and again over days and weeks.
Then change sources.
The 650's are not the greatest resolving cans out there, but listen for the little things, soundstage/imaging cues, brush strokes on cymbals, an acoustic bass, plucked or picked, speed, dynamics, contrast between notes, decay, pick a couple of favorite, well known songs and A/B them (pick some well recorded acoustic).
I'll just let it break in and see how it is in a week in a half and decide from there.