I think XML is the way to go, I'm actually using a DataTable within a DataSet to allow for intellisense. I am actually storing the settings (for this scenario) in the database associated to the users ID, storing the information as binary (compression and converted to byte array). The fun part of what I've done was also embed this into the My namespace. So I have My.AppName.Settings.SettingName. Has the same methods as My.Settings such as Load, Save, Reload, Reset. Was a little bit painful and some work, but it sure makes it nice to use when building the app.
Just seeing what others are using to store complex settings/preferences/options areas. Sharing ideas.