yes, the itunes library is a file on your hard drive, each item in your library has title, artist, and so on. Also on that list is the file location.
so itunes doesn't really scan the movie folder, as much as has an entry and knows where to look for a file.
-one thing to be aware of...
if you both download the same movie from the iTunes store, you will have 2 copies on your drive. "Titanic.mp4" and "Titanic (1).mp4". itunes/finder will add the "(1)" automatically to the one that gets added second, and each itunes library will know which one belongs to it (Bob's library will point to titanic.mp4, Mary's will point to "Titanic (1).mp4")
But... If Bob adds a movie to his library. Then Mary goes to the shared folder and adds that file instead of getting it from a location outside of the shared folder, then you will have one copy, and both libraries will point to the same file.