There's a limited form of re-initialization, but only for the swcodec playback system (e.g., to allow changes to the crossfade settings).
To allow a full re-initialization would probably require a fairly big restructuring of how Rockbox is initialized and how the buffer allocations are made. But getting the buffer allocations done in the right order isn't trivial, and has been the source of more than one hard to find bug, so a cleanup in this area could be nice.
Note that any change to a buffer-related setting would then cause playback to stop, at least temporarily, and any music would need to be re-buffered. So there are drawbacks too.