Plasma nitriding is widely used in various industrial applications to improve surface hardness and wear properties. Especially for tool steels, it is also used to improve the support and adhesion of diamond-like carbon (DLC) coatings. The properties of the nitrided zone produced by plasma nitriding are influenced by the applied process parameter, in particular temperature and time. However, for high-alloy tool steels, a deeper understanding of the underlying diffusion processes of the nitrogen and the interaction with the existing microstructure, as well as the effects on the case depth is still lacking. Therefore, in this study, specimens of high-alloy tool steel X153CrMoV12 were plasma nitrided at varying temperatures (480 °C, 520 °C, 560 °C) and treatment times (2 h, 4 h, 16 h). The resulting nitrided zones were investigated by optical and scanning electron microscopy (OM and SEM), depth-dependent glow discharge optical emission spectroscopy (GDOES), X-ray diffraction (XRD), and hardness measurements to characterize their microstructure, chemical composition, and hardness depending on the process parameters. The distribution of carbides (M7C3), e.g., chromium carbides, affects the diffusion of the nitrogen and the layer growth. An increase of temperature and duration leads to an increased layer thickness. The composition of the compound layer is, e.g., influenced by the process parameters: ε nitrides (Fe2–3N) occurred preferentially at lower temperatures, while γ′ nitrides (Fe4N) appeared mostly at higher temperatures. In order to investigate the influence of the carbides of the high-alloy tool steel on the nitriding process, a new methodology was developed by means of finite element analysis (FE), which makes it possible to analyze this influence on the development of the nitrogen concentration profile. This methodology makes it possible for the first time to map the heterogeneous nitrogen evolution and distribution.