If you considered scalability and are 100% positive that it's only going to be a max of 20 values, and the nature of the values is such that you could store in an XML file you should explore storing them in the App.config (or Web.config) of your application. Or store them in an external XML file of your choice if you wish - .NET has extensible support for manipulating XML files so the overhead is minimal in the case of a few records.
But if you think that your application may evolve and need to store more values in the future, or you want to provide some access restrictions to the values, then you should look into using some form of database. It's just better in the longer run..