Camera
I think that you should consider the Nikon D5000 body only and purchase the Nikon 18-200 lens with it.
The kit lenses that come with the Canons are useless as far as quality goes.
The Maxtrix metering system in the Nikons is very accurate especially in backlighting situations. I think that you should get your sister to familiarize herself with using flash and understanding "backlighting" as well as when to use "fill flash".
I am sure that there will be lots of photos taken at sunset as it is the most dramatic lighting but without the proper use of flash photography, you and your fiance will be silhouette.
Although the 18-200 lens isn't prime, it is VR and has ED glass which will help with photo sharpness. But most importantly, the zoom range makes it very convenient to compose without having to change lenses all the time.
I agree that Primes are much better for sharpness but having 2 or 3 Primes to add to the mix of using a unfamiliar camera, will only contribute to confusion. As well, Primes are very heavy to carry around.
Also, shoot in RAW so that you can make exposure changes and White Balanace Changes later. RAW's exposure control can rescue when you have underexposed photos of 1 to 2 f stops.
For ISO, I would commit to 200 ISO, (100 ISO if it's really sunny and bright and only outdoors) during the day if you end up wanting to enlarge the photos and go 400-800 for the night shots. Although these cameras have ISO settings to 3200, I have never shot that high and can't comment on the noise that may occur.
For artistic reasons, never have the subjects straight in the middle. Section the frame into thirds and have the subjects positioned in the left or right but usually never in the middle. This process adds dynamic viewing. You will need to learn how to use the Focus Lock feature to do this unless you know how to move the focus boxes around in the camera using the control pads.
Because you are shooting digital, buy lots of memory and go crazy shooting everything and anything. Change angles of view, so shoot low and vice versa, shoot high looking down. And for children, make sure you are shooting at their height so bend your knees and you will get some great candid shots.
When the vows are being done, take a few pictures of the bride and groom but have a look around the audience for the emotional photos. Usually, it's the brides parents who will have the tears. This will be the most powerful and emotional image of the day if you can capture it.
I'll add some more tips later.
Cheers.
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