Any suggestions on mixing ssd and hdd in btrfs

You could similarly create an independent Btrfs filesystem on the SSD (or rather, on a new LUKS device on the SSD), set it up to be automounted, and add another file-reflink Qubes OS storage pool somewhere on the mountpoint.

+1

This is just a guess but maybe Btrfs would decide based on whatever happens to be the PID of (one of) the kernel thread(s) servicing the xen-blkback device corresponding to the VM volume?