The shale of the Lower Cambrian Shuijingtuo Formation, as a key target for shale gas exploration in the Western Hubei region, possesses favorable conditions such as great thickness, high organic matter abundance, and moderate thermal maturity. However, the unclear mechanisms governing pore development have constrained sweet spot prediction, and there is a lack of quantitative characterization of the synergistic effects of multiple factors on pore development. To address the scientific questions of how multiple factors synergistically influence pore development and how to quantitatively evaluate the reservoir performance of different lithofacies, multi-scale experimental methods, including field emission scanning electron microscopy (FE-SEM), gas adsorption, high-pressure mercury intrusion, and fractal dimension analysis, were comprehensively applied in this study. Research indicates that fractal dimension positively correlates with TOC and micropore development, while negatively correlating with clay mineral content, serving as an effective indicator for characterizing the complexity of shale pore structures. Siliceous minerals resist compaction and preserve pores through rigid framework support, whereas clay minerals inhibit pore development through compaction and cementation, with carbonate minerals having a relatively limited influence. Higher TOC content drives the expansion of pore volume and specific surface area, predominantly within the micro-mesopore range. This results in a reduction of the average pore size. The shale pore system is synergistically controlled by a ternary mechanism of “rigid mineral support–organic matter pore generation–clay mineral inhibition,” with the configuration quality of these three factors directly controlling reservoir quality. To quantify the differences in reservoir properties among different lithofacies, a semi-quantitative evaluation model centered on the “Anti-compaction Index (ACI)–Organic Pore Contribution Index (OPCI)–Cementation and Filling Intensity Index (CFI)” was constructed. The evaluation results indicate that the highly organic siliceous shale (HS facies), characterized by an optimal synergistic configuration of “high OPCI, high ACI, and low CFI”, this lithofacies represents the optimal reservoir facies within the study area. This model enables the quantitative evaluation and comparison of reservoir performance across various shale lithofacies, providing an operable geological-quantitative basis for shale gas sweet spot prediction and favorable area optimization in the Western Hubei province.