Well, designing attractive application depends on your creativity. You can design an app in a simple way using attractive colors for FG and BG. Not a lot of colors though. By simple design I mean using at most two or three colors across the application. And the design should be consistent.
Its not about using complex graphics (created in PS).
The other way to do is to use GDI+ - if you have any knowledge of it. Here is the link http://msdn.microsoft.com/en-us/library/windows/desktop/ms533798(v=vs.85).aspx.
