Welcome to the boards! I was using a blackberry courtesy my old company for 2 years. It was my first smartphone and it served me well (especially since it was free). However, after starting at a new company, I didn't get the free phones anymore and to be honest, was quite happy as I could get the phones I wanted. At first I went to the Motorola Atrix but after some frustrating weeks with the scum known as AT&T, decided to turn my phone in to get the tbolt and have never been happier. Here are some tips off the top of my head.
1. Your battery will suck if you're on 4G at all times, turn it on to 3G or get the extended batteries (there is a 1700 mah battery that just came out and does not affect your phone size and also a 2750 mah battery that increases the size of your phone).
2. Go to the android market. This is really where android/iphone outshines blackberry. The amount of app availabilty really doesn't compare. When I like to do is view all apps in the market, and then click on top free as those are the top downloaded/rated apps out in the world so you know some of them have to be useful. Same with top free games.
3. Make use of your 7 home pages. These home pages set android apart from iphone in a great and better way. Whereas on the iphone, your home page is just all your apps (and folders if you choose), you can set your home pages to display so much more. This includes weather, stocks, news, your email, mint.com if you use it, your music player, contact shortcuts etc. I would spend some time adding widgets to your home page to make it the way you'd want.
4. Animated wallpapers will pwn your battery life.