Hi,
There should be a Documents folder in the ZStack installation directory. The document "Z-Stack User's Guide - CC2530DB.pdf" should tell you everything you need to get simple commands sent between 2 devices. The Demo configuration that you are instructed to use, uses jumpers on GPIO's to select which device is Coord, if you prefer you can select at program time by select CoordinatorEB, RouterEB or EndDeviceEB instead of DemoEB.
More information about the message flow and other sample application can be found in "Z-Stack Sample Applications.pdf".
Regards, TC.