A GEANT4 based Monte Carlo simulation has been successfully utilised to calculate peak efficiency characterisations and cascade summing (true coincidence summing) corrections in two source geometries commonly used for environmental monitoring. The cascade summing corrections are compared with values generated using an existing (validated) system, and found to be in excellent agreement for all radionuclides simulated. The calculated correction factors and peak efficiencies were also tested by analysing well defined sources used in the operation of the International Monitoring System, which undertakes radionuclide monitoring for verification of the Comprehensive Nuclear-Test-Ban Treaty. All abundances of the radionuclides measured matched the values that were previously determined using proprietary software. Using GEANT4 in this way, cascade summing corrections can now be extended to complex detector models and source matrices, such as Compton Suppression systems.