As climate extremes increasingly threaten global food security, precision tools for early detection of crop stress have become vital, particularly for root crops such as potato (Solanum tuberosum L.) and sweet potato (Ipomoea batatas L. Lam.), which are especially susceptible to environmental stressors throughout their life cycles. In this study, plants were monitored from the initial onset of seasonal stressors, including spring drought, heat, and episodes of excessive rainfall, through to harvest, capturing the full range of physiological and biochemical responses under seasonal, simulated conditions in greenhouses. The spectral data were obtained from regions of interest (ROIs) of each cultivar’s leaves, with over 3000 data points extracted per cultivar; these data were subsequently used for model development. A comprehensive classification framework was established by employing machine learning models, Support Vector Machine (SVM), Linear Discriminant Analysis (LDA), and Partial Least Squares-Discriminant Analysis (PLS-DA), to detect stress across various growth stages. Furthermore, severity levels were objectively defined using photoreflectance indices and principal component analysis (PCA) data visualizations, which enabled consistent and reliable classification of stress responses in both individual cultivars and combined datasets. All models achieved high classification accuracy (90–98%) on independent test sets. The application of the Successive Projections Algorithm (SPA) for variable selection significantly reduced the number of wavelengths required for robust stress classification, with SPA-PLS-DA models maintaining high accuracy (90–96%) using only a subset of informative bands. Furthermore, SPA-PLS-DA-based chemical imaging enabled spatial mapping of stress severity within plant tissues, providing early, non-invasive insights into physiological and biochemical status. These findings highlight the potential of integrating hyperspectral imaging and machine learning for precise, real-time crop monitoring, thereby contributing to sustainable agricultural management and reduced yield losses.