Solved it!
Tried a bunch of things and have worked out a configuration that allows Runeaudio to happily mount and view/index NFS shares from my Synology Diskstation.
Note: although this config works, I'm unsure as to if this makes the NAS more insecure than necessary, feel free to critique!
On the RPI I left the MPD Daemon user : group setting as "root:root".
In the Diskstation's File Services settings, I unticked "Apply default UNIX permissions" in the advanced settings tab for NFS.
I removed the password from the "Guest Account" on the Diskstation by turning off password strength controls.
In the Shared Folder settings I gave the Guest Account read access in permissions - I did not turn on "Advanced Permissions".
Here is a screen shot of the NFS settings I used, note: I did not use the squash settings:
Hopefully this can save someone hours of frustration!
Good luck fam.