Recommendations:
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Create shares for your media using names meaningful to you.
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Don’t use any pre-defined Synology shares - They conflict
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After installing but before setting up library sections, Control Panel - Shared Folders - Give user Plex permission to read the media.
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Give this a read to familiarize yourself with the process.
Installation & Setup of Plex Media Server on Synology -
Proceed with the rest
a. Download and install the X86_64 version from plex.tv/downloads.
b. Package Center – Manual install (upper right)
c. Give it the SPK file you just downloaded.