See Synology FAQ 15: Claiming & Connecting to a troublesome Synology server.
If that does not work, please provide a set of server log files (FAQ 1).
- In Package Center, stop Plex Media Server.
- In File Station, go to /PlexMediaServer/AppData/Plex Media Server. Compress the Logs directory to Logs.zip.
- Upload the zip file to the thread (Drag it into the message window. It will insert at the cursor location).