Agentic Retrieval-Augmented Generation (Agentic RAG) enhances the processing capability for complex tasks through dynamic retrieval and adaptive workflows. Recent advances (e.g., Search-R1) have shown that outcome-supervised reinforcement learning demonstrate strong performance. However, this approach still suffers from inefficient exploration, sparse reward signals, and ambiguous global reward feedback. To address these challenges, we propose DecEx-RAG, which models RAG as a Markov Decision Process (MDP) incorporating decision-making and execution, while introducing an efficient pruning strategy to optimize data expansion. Through comprehensive process-level policy optimization, DecEx-RAG significantly enhances the autonomous task decomposition, dynamic retrieval, and high-quality answer generation capabilities of large language models (LLMs). Experiments show that DecEx-RAG achieves an average absolute performance improvement of $6.2\%$ across six datasets, significantly outperforming existing baselines. Moreover, the pruning strategy improves data construction efficiency by nearly $6 \times$, providing an efficient solution for process-supervised RAG training. The code is available at https://github.com/sdsxdxl/DecEx-RAG.