Hi Josh,
The best thing to do when using a color wheel is to match opposite colors. Opposite colors on the color wheel always go together well.
Also, when it comes to making a template, try to only pick 3 or at most 4 colors for the template. For example AbyssUnderground uses 4, Black, White, Blue and Orange. Choosing too many colors can make things look messy. Also make sure the colors compliment each other. My Blue and Orange do go well together so its not a problem.
On this color wheel you can see that blue and orange do go well together as they are fairly opposite each other. White and Black are not included on the wheel because they fit with all colors anyway.
Hope this helps. Come on MSN if you have any questions about it :-)