i'm assuming you are going to the wedding as a guest not the official 'tog. In which case from the shots point of view I'd look at getting candid shots and different shots to those the photographer is taking. While the group shots are being taken maybe stand back with a telephoto lens and go for head and shoulder shots. The main thing is not to get in the way of the official photographer, he is being paid to do a job and doesn't need someone else with a dslr shooting over his shoulder.
I'd certainly shoot raw, Brides dresses and dark suits are an exposure nightmare so the greater latitude raw gives for highlight recovery could come in handy.
I shoot in AV or manual depending on what mood I'm in and how tricky a shot is to meter. When using flash I use AV with a high iso as much as possible to keep the flash input to a minimum and use the ambient light as much as possible. Don't use your flash during the service, most Vicars and registrars take a dim view of it even with the official photographer.
Hope that helps, but the main thing is enjoy the day!
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