Open the config.config file.
In config/smartThingsEndpoints fill in your API token and endpoint urls.
Be sure to keep the /statechanged/on* at the end of the urls.
If plex and this application is not running on the same server then enter the url to the session status page of your plex server in the config/plexCheck/@plexStatusUrl attribute.
Configure the rest of the file to your likings.
You can now run the application and the smartapp should be notified whenever any media plays on plex.
If anything isn’t working you can try enabling some extra debug output by adding the d1 or d2 arguments. E.g. running Plex2SmartThings.exe d1 from the command line.