Files Unavailable to play, but they exist and are seen in Get Info

It could be indeed an issue with access permissions.
However, trying to diagnose access permission issues using the Windows file explorer won’t help much, when the Plex server is running in a Synology NAS (which uses Linux).

Are you familiar with this? Synology FAQ - Questions, Answers, and How-To's
I presume Q19 would be most applicable to your use case.
If you just recently upgraded from DSM 6 to DSM 7 or DSM 7.2.2, Q26 and Q34 might also be relevant.