Tough one. I don't think I can come up with one single most important thing, there are so many equally important things. So, for your first time:
1. Make a list (in order) of the shots you need to take, and what special (if any) shots the bride would like you to take. Things move fast and it's easy to miss something, so go by the list.
2. Be prepared to shoot at all times. Even if it's not on the list. If you think it would be a good shot, take it.
3. Don't be shy, but don't be rude. Get in there and shoot. It's what you are supposed to be doing.
If guests get in your way, move around them or ask them to move aside and let you get this shot.
4. Be on time. Be prepared. This is not the time to be fooling around with your equipment.
5. Take plenty of shots. It's better to have too many than not enough.
6. This may be the most important. I would not shoot a wedding with just one camera, lens and flash. I realize you are not a professional wedding photographer, but if something happens to your gear, you're done! Try to borrow a second camera setup if you can. Even a point and shoot can save the day.
7. Be sure you know how to operate your camera and if you borrow a second, be sure you know how to operate it.
8. Make sure your sister-in-law understands this is your first wedding shoot and although you may get professional results, you are not a seasoned pro (yet).
9. If you have a wide angle lens, bring it. You may find it very useful.
10. Don't use flash during the ceremony in the church unless you clear the use of flash first with the church.
11. Stay off the ALTER. Personally, I think it's rude.
12. A "flip flash bracket" is always useful.
These thoughts are just the tip of the iceberg. It would be easier if you had specific questions
Oh yea, take a look at "Planet Neil". He is a wedding photog. You may find his site interesting.
Good luck, have fun, lets see some pix when you are done.