Tropical Capsicum chinense is known for its strong leaf cooling capacity and stomatal responsiveness under high-temperature conditions. To better understand whole-plant acclimation strategies, we examined leaf-level physiological responses—including stomatal behavior and water potential under atmospheric stress based on combinations of temperature and humidity. Particular attention was given to signaling mechanisms beyond conventional VPD-based models and age-dependent differences in leaf responses. Under high-temperature and low-humidity conditions, transpirational cooling was markedly enhanced, lowering leaf surface temperature by up to 6.3 °C. This cooling effect contributed to the maintenance of high leaf water potential across canopy layers and sustained photosynthetic activity. In contrast, under moderate temperature and low humidity, stomatal closure occurred despite low intercellular CO₂ concentrations, suggesting the involvement of humidity-specific signaling mechanisms. Additionally, leaf age influenced stress sensitivity, with lower-position leaves showing greater vulnerability to senescence and water imbalance. These findings demonstrate that temperature and humidity act interactively to shape leaf water regulation and stomatal behavior. The results provide new insights into plant physiological adaptation under atmospheric stress and contribute to the refinement of stomatal response models and climate-resilient crop management strategies.