I also pre-ordered the collectors edition at Best Buy. Is there a way to give my standard version to my wife and use the collectors version for myself?
The Collector's Edition is only available from retail, and that means to play as soon as possible you'll want to hit a midnight release to pick it up. We don't have any plans to release a digital CE, it's a retail-only kind of thing. But! you may have a few options.
If you have the WoW Annual Pass (or go sign up for it now) you get a free digital copy of Diablo III. This will give you the game right at midnight, you can go download right now, all that stuff. Then, when you pick up your CE, you can overwrite the standard edition license with the CE license and you'll be granted 4 months of game time (more or less equivalent to the cost of the standard edition). So that's a good option. More info also available in the Annual Pass FAQ.
Alternatively, you can get the digital version now, play right at midnight, overwrite your license with your CE when you pick it up, and then contact our support department. In most situations they'll be able to grant you a new standard key, which you can then give to a friend, or whatever.
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