Some sort of scripting language would be best IMO. I've done GUI programming in BASIC, Java, C and C++ as well as several scripting languages, and I was more productive by far with a scripting language like Python or Tcl.
python is a very good choice for a GUI language because it has several toolkits you can easily choose between. For example, Tkinter (based on tk) is probably already installed on your system. Two other popular choices are wxPython and PyGTK.
All three of those are roughly equivalent in power. Some are a little simpler to use, some look prettier, some are more stable than others, but any of them would be a fine choice for learning. Once you spend some time with one of them you'll have an idea of what they can or can't do, and that will be a good time to read up on the other toolkits to see if they meet your needs any better.