I can use my function key+stop, next, previous, etc to control totem using my Keyboard. Can I map these settings entirely to vlc?
Yes, if you want to enable media controls for VLC in Ubuntu 10.10 ...
(I can't speak for other releases, anyone?)
... you will need to unset the media control keyboard global shortcuts in order to use them with VLC.
1) Open Keyboard shortcuts settings. Disable media play/pause/skip/reverse and whatever else you wish to use with VLC.
2) Open VLC preferences and set shortcuts for the keys you want to use. Tools>preferences>Hotkeys tab. Change "Global" setting: Double-click "global" list item area: hit according media key. hit "apply", "save".
3) Restart VLC.
This question is answered on launchpad: https://answers.launchpad.net/ubuntu/+source/totem/+question/109827