Plex Server not working on Synology

Do not modify permissions for the PlexMediaServer shared folder. Doing so can easily break Plex.

As @dbirch mentions, give the system internal user PlexMediaServer at least read only permission to your data files.

Some documents that may help:
Installation & Setup of Plex Media Server on Synology

Synology FAQ - Questions, Answers, and a few How-To’s