Setting MIME Types
Unlike some other browsers, Firefox does not provide a way to set up new MIME Types using the Preferences menu. You're allowed to review them or disable them, you just can't make new ones.
In order to set up a new MIME association, you must first try to download a file of that type. Firefox will offer you a dialog box giving you a choice of either downloading the file or opening the file. By choosing to open the file, you will be offered a file browser dialog to specify the application. Once you have specified the appropriate application and closed the file browser, remember to check the "always take this action when downloading files of this type" check box.
Once you've okay'd this dialog box, your new MIME type has been set up.
Modifying Firefox's Context Menus
Here's a way to customize Firefox by adjusting the menus to the options that you think are important or convenient: Mark Irons' Tech Notes
Google Toolbar for Firefox
Google Toolbar Spellcheck Problem
But, what about reconfiguring a mime type association?
My Firefox seems to associate MP4 with Quicktime plugin, but I would like to associate it with another tool. How? After consulting a lot of pages, I don't figure it.