I'm with Alex here when it comes to 32 vs 24. Go with the native resolution for the BL5s. There isn't any source material available in 32-bit anyway.
But Pure Music is heartily recommended by me. I have it set up from my MacMini through a digital router to the BL5s, and I do hear a noticeable difference between playback detail through PM compared to straight from the integrated iTunes/QuickTime. I like what I hear from PM better.
BTW - I connected my BL5s to a Beomaster 7000 through Powerlink, the BL5s are getting their sound signal from the MacMini, through the path described above. As the BL5s give priority to an S/PDIF signal, when I press CD on my Beo4, the Beomaster can be used to control the volume of the speakers, and on/off - while the signal they receive is routed straight to them via S/PDIF. Best of both worlds as I get a precise control of volume and integration, while giving the speakers the best signal. When I press Radio, Tape or other options, the Beomaster is used to route those signals to the speakers through PL.
But I now have excellent iTunes/Pure Music playback from my NAS, as well as Spotify playback from the mini to the speakers, both through the S/PDIF IN on the BL5s.
Speakers in Option 0.