Please have a look at this Question
Especially, try out the following code from an answer there:
using System.Configuration; // Add a reference to System.Configuration.dll
...
var path = ConfigurationManager.OpenExeConfiguration(ConfigurationUserLevel.PerUserRoamingAndLocal).FilePath;
Also, check out this overview, perhaps you ran into some limitation which is not easy to tell from your question.
This codeproject article might be of some help.