From the Wiki I got the impression mounting network shares with autofs was the way to go. But in that case the mapped folders are no longer on a remote server, as far as Kodi is concerned. So no WoL.
I did just find a script for wake.py though. Trying that now.
My main concern is #1 though, I really have no idea how to handle that just yet.
P.S. I forgot to mention the MySQL database for Kodi is also running on the NAS server.