This has been discussed around here at least a couple of times and many have learned their own techniques of sorts. I have done plenty of polishing from small parts to rough aluminum intakes to wheels and there are many different products and ways to accomplish the desired finish and look.
If your wheels are already smooth and just dulling, then you can use any of these suggested above and end up with good satisfying results. I Have never personally tried the Simichrome polish yet and will probably order some just to see how it works on some different metals, I have heard high regards for the product. Definitely curious as to how well it works on larger surfaces like wheels. The product description states to use it very sparingly, which tells me it's probably good stuff.
Now the Blue Magic Jon mentioned I have used for years and it works well for its intended purposes. It will definitely shine up slightly dull to dull surfaces by hand or with a machine.
Another product many people like is the Mothers Powerball. I'm sure someone will attest to it.
If you have pitting, then the real elbow grease comes into play. I will generally work using the appropriate airway buffing wheels attached to a heavy duty polisher, utilizing brown and green rouge. Next use a cotton muslin and white rouge. Clean up and you also go with a final finish of metal polishes mentioned above using a nice micro fiber polishing towel. When going this extensive, most people just pay to have it done since it is kind of costly to get set up for your self and can also be dangerous.
I do like to do my own polishing, but sometimes will pay another pro when price and timing are in order.
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