In a fleet of mission-critical systems, maintaining high availability for each individual system is vital to ensure consistent fleet readiness to meet mission demands. This study introduces a novel mission assignment strategy aimed at actively aligning maintenance schedules within each system to maximise opportunistic maintenance potential, thus enhancing system availability. However, solely focusing on system-level assignments may result in simultaneous maintenance needs across the fleet, leading to resource conflicts. The proposed strategy addresses this issue by coordinating mission assignments to consider both the alignment of schedules within a system and the even distribution of schedules among systems to prevent fleet-level conflicts. Two operational conditions, intra-system and inter-system balance, are defined to evaluate the criticality of each system at both system and fleet levels. Based on these conditions, scheduling rules are developed to determine assignment priority across the fleet in a two-phase process. Simulation studies demonstrate the effectiveness of this approach, showing a 2% improvement in system availability, equivalent to a two-month reduction in downtime across the fleet over a one-year period. The results underscore the advantages of the proposed strategy in optimising maintenance operations in complex fleet environments with diverse mission requirements.