I currently have an app.config in an application of mine set up like so:
You are almost there - you just have nested your MajorCommands a level too deep. Just change it to this:
And then the following will work for you:
var section = (Hashtable)ConfigurationManager.GetSection("MajorCommands");
Console.WriteLine(section["Reset"]);
Note that this is a Hashtable (not type safe) as opposed to a Dictionary. If you want it to be Dictionary
you can convert it like so:
Dictionary dictionary = section.Cast().ToDictionary(d => (string)d.Key, d => (string)d.Value);