Simulation studies of thermoluminescence (TL) and other stimulated luminescence phenomena are a rapidly growing area of research. The presence of competition effects between luminescence pathways leads to the complex nature of luminescence signals, and therefore, it is necessary to investigate and validate the various methods of signal analysis by using simulations. The present study shows that in simulations of luminescence signals originating from multilevel phenomenological models, it is not possible to extract mathematically the individual information for each peak in the signal. It is further shown that computerized curve deconvolution analysis is the only reliable tool for extracting the various kinetic parameters. Simulation studies aim to explain experimental results, and therefore, it is necessary to validate simulation results by comparing with experiments. In this paper, testing of simulation results is performed using two methods. In the first method, the influence of competition effects is tested by comparing the input model parameters with the output values from the deconvolution analysis. In the second method, the agreement with experimental results is tested using the properties of well-known glow peaks with very high repeatability among TL laboratories, such as the 110 °C glow peak of quartz.