Optimizing the operation of photovoltaic (PV) storage systems is crucial for meeting the load demands of parks while minimizing curtailment and enhancing economic efficiency. This paper proposes a multi-scenario collaborative optimization strategy for PV storage systems based on a master–slave game model. Three types of energy storage system (ESS) application scenarios are designed to comprehensively stabilize PV fluctuations, compensate for load transfers, and participate in the frequency regulation (FR) market, thereby optimizing the overall operational strategy of PV storage systems in parks. The upper-level objective is to maximize the park operators’ profit, while the lower-level objective is to minimize the user’s power supply costs. Case studies demonstrate that this strategy can significantly increase the economic benefits for park operators by 25.8%, reduce user electricity expenditures by 5.27%, and lower curtailment through a load response mechanism, thereby promoting the development and construction of PV storage parks.