The paper presents the scope of applicability and the usefulness of the method of predicting crystalline structure of castings using a commercially available system called Calcosoft CAFE. The influence of individual values of the parameters of the thermal model and the model predicting the structure (phenomenon of nucleation and crystal growth), and the method of interpretation of the results were identified. In simulation studies, it is important to use reliable and validated material database, under appropriate conditions. It is necessary to predict the properties of castings with a comprehensive, new and practical approach to modelling the formation of phase components of structure in terms of both macroscale and microscale phenomena (Multiscale and Multiphysics). Therefore, in this paper, the experimental-simulation validation of the CAFE code was undertaken. The tests were carried out on castings solidifying under various heat transfer conditions controlled by mould materials such as: a homogenous mould made of moulding sand, moulding sand with chill, and mould made of insulating mass with chill. These conditions directly influence the structure formation. The method of validation of the structure was determined in terms of its three parameters, i.e., the degree of refinement of the crystals, the location of the columnar-to-equiaxed transition zone—CET and the angle of the crystals. The above tests enabled to extend the content of databases, which often lack the necessary values of parameters used in modelling, e.g., crystallization of a specific alloy under given conditions (sand casting, chills or laser surface treatment). On this basis, the basics of correlating the simulation results on a micro- and macroscale were generalized, the limits of the application of individual parameters (mould, alloy materials) and their impact on the structure formation were determined. It resulted in the extension of the database for simulation calculations.