Adding multiple iTunes categories *might* get your podcast featured in any of those categories. Apple picks featured shows by hand. If they like your show, and want to feature it, but don't have any room in your primary category, they *might* feature your show in one of the secondary categories you've chosen.
The show will still have to be relatively relevant to those secondary categories in order for them to choose it. If it's a show about technology, and they want to feature it but don't have any feature slots available for that as a primary category and you've got the show listed in comedy as a second category (and it's clearly not a comedy show), Apple probably won't feature it in the comedy category.