I live right in Bourbon country. I didn't really start drinking any whiskey till I moved out here, now I just about rotate between beer and Bourbon depending on the type of drinking I'm doing (Dinner vs. Sports vs. Bar etc.)
I'm guessing the smoother more simple flavors of the scotches will probably suit a Vodka Drinker more than bourbon, but if you were tending to mix with sweeter mixers, you might try it. Maker's Mark is a reasonible place to start, but, if you can find it, Four Roses is delicious. Great Maple Syrup tones.
Also, If you like Mojitos, a Mint Julep is basically a bourbon Mojito. The Derby is coming up in a couple weeks, buy yourself some bourbon and mint, find a way to put a couple bucks on a horse, and enjoy. :D