OK, let's start checking for the error.
In my Database, the information in the VolumeLabels is as I described, literally the Windows Hard Drive volume name (regardless of whether it is on the client pc or NAS), No good way to map it to path because in a few cases I have different paths on same drive. Another issue I had is that my Database did not map exactly as yours (fields/columns in a different order), so pulling information by column number led to incorrect information.
I found a workaround to the above by simply manually replacing the info in the VolumeLabel field with the correct path data (from ImportPathes table) and by creating a new database with the columns reordered to match your mapping, giving me partial success. The TVShow.nfo (Series information) is correctly written and the TVShow fanart/etc. is correctly copied; HOWEVER: I am having issues with the episode information.
I discovered that the episode data retrieved (season and episode numbers) don't match the local episodes, so that either the information written to the episode nfo file is for the wrong episode (correct series but wrong episode, ex: episode 7x7 has data from episode 2x1) or the app crashes (I assume because it is attempting to retrieve non-existent information)
I found the code that is causing my problem and have been attempting to modify/rewrite some of the Autoit code that does the season/episode matching of the local_episode and online_episode tables but I still need to wrap my head around the syntax and function of some of the Autoit code (specifically how to build a new array from the online_episode table that matches Series, Season, Episode)