Minimizing the setup costs caused by color changes is one of the main concerns for paint shop scheduling in the automotive industry. Yet, finding an optimized color sequence is a very challenging task, as a large number of exterior systems for car manufacturing need to be painted in a variety of different colors. Therefore, there is a strong need for efficient automated scheduling solutions in this area. Previously, exact and metaheuristic approaches for creating efficient paint shop schedules in the automotive supply industry have been proposed and evaluated on a publicly available set of real-life benchmark instances. However, optimal solutions are still unknown for many of the benchmark instances, and there is still a potential of reducing color change costs for large instances. In this paper, we propose a novel large neighborhood search approach for the paint shop scheduling problem. We introduce innovative exact and heuristic solution methods that are utilized within the large neighborhood search and show that our approach leads to improved results for large real-life problem instances compared to existing techniques. Furthermore, we provide previously unknown upper bounds for 14 benchmark instances using the proposed method.