Query-product relevance prediction is fundamental to e-commerce search and has become even more critical in the era of AI-powered shopping, where semantic understanding and complex reasoning directly shape the user experience and business conversion. Large Language Models (LLMs) enable generative, reasoning-based approaches, typically aligned via supervised fine-tuning (SFT) or preference optimization methods like Direct Preference Optimization (DPO). However, the increasing complexity of business rules and user queries exposes the inability of existing methods to endow models with robust reasoning capacity for long-tail and challenging cases. Efforts to address this via reinforcement learning strategies like Group Relative Policy Optimization (GRPO) often suffer from sparse terminal rewards, offering insufficient guidance for multi-step reasoning and slowing convergence. To address these challenges, we propose TaoSR-AGRL, an Adaptive Guided Reinforcement Learning framework for LLM-based relevance prediction in Taobao Search Relevance. TaoSR-AGRL introduces two key innovations: (1) Rule-aware Reward Shaping, which decomposes the final relevance judgment into dense, structured rewards aligned with domain-specific relevance criteria; and (2) Adaptive Guided Replay, which identifies low-accuracy rollouts during training and injects targeted ground-truth guidance to steer the policy away from stagnant, rule-violating reasoning patterns toward compliant trajectories. TaoSR-AGRL was evaluated on large-scale real-world datasets and through online side-by-side human evaluations on Taobao Search. It consistently outperforms DPO and standard GRPO baselines in offline experiments, improving relevance accuracy, rule adherence, and training stability. The model trained with TaoSR-AGRL has been successfully deployed in the main search scenario on Taobao, serving hundreds of millions of users.