I currently have an app.config in an application of mine set up like so:
I would probably treat the config file as an xml file.
Dictionary myDictionary = new Dictionary();
XmlDocument document = new XmlDocument();
document.Load("app.config");
XmlNodeList majorCommands = document.SelectNodes("/configuration/DeviceSettings/MajorCommands/add");
foreach (XmlNode node in majorCommands)
{
myDictionary.Add(node.Attributes["key"].Value, node.Attributes["value"].Value)
}
If document.Load doen't work, try converting your config file to xml file.