You should be able to do this the old-fashioned way, by right-clicking a file of the type you want VLC to play, and selecting VLC as the player to use in the Open With.. menu item.
Alternatively, you can specify the mime-types you want VLC to handle by following the steps on the VLC wiki page: How to make VLC the default player. This procedure will work for any kind of media you wish to configure.
Have a look at my answer on how to change default apps on Ubuntu by configuring the mime-types. The file location might be different on Fedora, but the procedure should remains the same because it is how Gnome behaves.