I know a thing or two about LSR2335p - I own them, probably one of very few on this board
Yes, for best quality you'd want all digital domain volume control to be at 100%, that said, windows main volume control I still use.
To get best quality and illuminate buzz/noises you'd want to get external DAC.
I got good results with Audioengine D1 dac (toslink from pc) and shielded rca cabled, but balanced dac & cables should work as well, I just couldn't find anything really decent but one: Emotiva XDA-2 which I believe was cheaper before...