Holy hell gentlemen.
After a night (and half a day) of toil and "wtf's?"... I've found the issue. There were 2 "game folders" (identical) in the MAME folder. So, when poking around through Launchbox and looking for associations, it looked as if it was "pointed" to the correct place. However, it was pointing at an identical folder.
I cannot for the life of me figure out how that happened/can happen, without having "(copy)" after the name.
I actually am not even able to replicate it.
Thank you for all your comments last night! I appreciate the effort.
LAUNCHBOX IS BACK BABY!