There are several options, like the EntLib FileConfigurationSource, creating a custom Reader to read arbitrary config files, etc. I came across Mike Woodring's AppSettings implementation, which gives a pretty close approximation of how config file logic works. It doesn't use the new .NET 2.0 sections, but it's a good start and got my code working with minimal trouble.
Disclaimer The opinions expressed herein are my own personal opinions and do not represent my employer's view in any way.