The way I do it is this:
1) Rip the entire disk to your hard-drive. It eliminates the pause at the layer-break which can cause a/v synch problems.
2) Open the ripped folder with VLC, and select each episode through the DVD's normal menu. Clicking the "playback" menu on VLC while the episode is playing will tell you exactly which title goes with which episode
3) Hit the "previous title" button ( |<< ) to return to the main menu and select the next episode until you have all the episode title numbers identified.
Just grabbing the biggest titles won't always give you the correct results, as some series will include a title which combines all the episodes into one, others have special features that are pretty huge, and some even have the same episode appear multiple times under different title numbers. For example, you may only have 4 episodes on a disk, but have 8 large titles - one is all four episodes together, and three are just duplicates. Better to confirm which titles are associated with which episodes and only compile those to save a lot of time and space.
Also, I notice that on some series, the various episodes aren't always together and they aren't always in numerical order. Knowing which titles goes with which episode will help you get the names correct.
