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Raw and JPEG
Your approach to the white balance and Picture Style settings depends a lot on whether you use the Raw or JPEG formats on your camera. If you use JPEG, you have fewer options in post-processing; therefore, it makes sense to get the image as close to finished as possible in-camera. If you get the white balance and Picture Style settings correct, that means less post-processing work—always a benefit for photographers who dislike using computers or are short on time. You can even bypass the computer altogether and print directly to a PictBridge-compatible printer.
My approach is to use the Raw format, which has a number of benefits. The main advantage is that I can set the white balance and Picture Style options when I process the Raw file, so the decisions I make during the shoot are not final. I can fine-tune the settings when I process the image, working according to the needs of each photo.
I use Lightroom for most of my Raw conversions. One Lightroom feature that I really like is the "virtual copy" function, which makes it easy to produce more than one "interpretation" of a single Raw file. I sometimes make two versions of a single image—one with a warm color balance and another with a cool balance. I can also make another virtual copy to convert to black-and-white.
Color is a natural part of any subject, and it's easy to take it for granted. But thinking about color will improve your compositional skills and your photos. Start by developing an awareness of how color and light work together, and you'll develop a vision of how you want the colors of your subject to appear in the final image. Once you've decided on a goal, the white balance and Picture Style settings on your camera are the tools you need to help you get there.