Hi Will,
That's cool. I've never tried piCorePlayer, quite simply because I've had ZERO problems with the RPi, using Volumio (and also Moode), since day 1, so have no need to experiment.
In my set-up, to play music on the RPi, all I have to do is switch my hi-fi system on, and as my Macbook Pro will already have been on since first waking up in the morning around 8-9am (and which boots up and is fully operational in seconds), all I have to do is click once on a saved tab on my desktop, which takes me to Volumio, and the last piece of music I had been listening to before going to bed that night, and click play (or choose something else), and I'm away!
It's a piece of piss!
Marco.