You can find most of the keyboard shortcuts by taking a look at the menus. Additional hotkeys are defined in the section "Hotkeys" of your VLC preferences.
Some handy key combo's are:
- You can use the spacebar to start/pause the video.
- When in fullscreen you can use the escape key to exit the fullscreen state
- When you are watching a DVD and the video window is the frontmost window you can use the arrow keys and the enter key to navigate the DVD menus.
There doesn't seem to be any way to access the streaming wizard in the MacOSX version of VLC. In order to stream you have to use the Advanced Settings in the Open... dialogue box. The Streaming wizard will be present in the 0.8.4 release for MacOSX. Have a preview with the nightly builds.