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if you REALLY want to understand how it works you can always read
http://arxiv.org/pdf/1307.0996v1.pdf (final version here: IEEE Transactions on Nuclear Science Vol. 60 No. 4. August 2013.)
in which the authors introduce and alternative way to compute the radioactive decay in Geant4. However in order to explain their procedure they go a decent length at explaining the "nominal" Geant4 radioactive decay.
On the other hand if you just want to use the radioactive decay, You need to make sure you have the radioactive data installed in your computer and that the environment variable G4RADIOACTIVEDATA is correctly pointing at the right location.
Some documentation can be found here:
but that is not a good place to start (I think). I would probably suggest you to simply have a look at this:
The radioactive decay starts at slide 22/31