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- Open the gnome-vfs mime database, usually at /usr/share/mime-info/gnome-vfs.keys
- Search for the application type you want to modify (for instance, pdf)
- Ignoring all the language garbage, find default_action_type= either application or component. Component will try to use one of the items in the short_list_component fields, which are desktop-specific handlers. Application will try to use one of the items int he short_list_applications fields.
- Set whatever you want to use as the first app in each applications list. For example, pdf might say "acroread,gpdf,xpdf,ggv,gv"
- You might need to log out for changes to take effect.