5G New Radio (NR)-V2X, standardized by 3GPP Release 16, includes a distributed resource allocation Mode, known as Mode 2, that allows vehicles to autonomously select transmission resources using either sensing-based semi-persistent scheduling (SB-SPS) or dynamic scheduling (DS). In unmanaged 5G-NR-V2X scenarios, SB-SPS loses effectiveness with aperiodic and variable data. DS, while better for aperiodic traffic, faces challenges due to random selection, particularly in high traffic density scenarios, leading to increased collisions. To address these limitations, this study models the Cellular V2X network as a decentralized multi-agent networked Markov decision process (MDP), where each vehicle agent uses the Shared Experience Actor–Critic (SEAC) technique to optimize performance. The superiority of SEAC over SB-SPS and DS is demonstrated through simulations, showing that the SEAC with an N-step approach achieves an average improvement of approximately 18–20% in enhancing reliability, reducing collisions, and improving resource utilization under high vehicular density scenarios with aperiodic traffic patterns.