Wrote a console app to roll through the System.Configuration.Configuration["AppSettings"]
I don't think that this is an ArcMap thing, but if anyone has any experience with this please let me know..
Have you tried accessing the config settings using the built-in .NET functionality? The .NET runtime reads the application config file for you and provides an easy way to access the settings. In VB.NET, you can access the config settings using My.Settings.<setting>, where <setting> is the name of the config setting you want. In C#, this can be done using Properties.Settings.Default.<setting>.