Previous studies on Virtual Reality (VR)-enriched learning pointed out the advantages of immersive learning for the development of competencies. In the context of vocational education in vehicle painting, training opportunities are severely limited for many reasons. VR can be utilized to develop a comprehensive learning environment with authentic training tasks. Besides the need to train psychomotor skills, vehicle painting procedures are complex tasks requiring incremental training to develop knowledge, skills, and attitudes. This study aims to evaluate a VR training application for vehicle painting, focusing on the development of professional competencies regarding skills, knowledge, and attitudes. 47 apprentices participated in the evaluation study. A VR-simulated painting booth was developed based on the 4 C/ID model by van Merriënboer, where they dealt with typical painting jobs on 3D workpieces (e.g., car wings, engine hood). Within the descriptive-inferential study, no significant differences between the types of competencies were revealed. The training application supports the acquisition of skills, knowledge, and attitudes equally. Further results regarding usability, cognitive load, etc., are promising. The essential finding of this study is that the VR training application is generally suitable for supporting craftsmanship within the field of vehicle painting. Since training opportunities for apprentices in this context are often rare, VR offers a unique solution especially for skills training if it follows a proven instructional model for the development of competencies.