Retrieval-Augmented Generation (RAG) systems depend critically on retrieval quality to enable accurate, contextually relevant LLM responses. While LLMs excel at synthesis, their RAG performance is bottlenecked by document relevance. We evaluate advanced retrieval techniques including embedding model comparison, Reciprocal Rank Fusion (RRF), embedding concatenation and list-wise and adaptive LLM-based re-ranking, demonstrating that zero-shot LLMs outperform traditional cross-encoders in identifying high-relevance passages. We also explore context-aware embeddings, diverse chunking strategies, and model fine-tuning. All methods are rigorously evaluated on a proprietary dataset powering our deployed production chatbot, with validation on three public benchmarks: FiQA, HotpotQA, and SciDocs. Results show consistent gains in Recall@10, closing the gap with Recall@50 and yielding actionable pipeline recommendations. By prioritizing retrieval enhancements, we significantly elevate downstream LLM response quality in real-world, customer-facing applications.