Understanding the mechanisms and spatial correlations of crystallographic symmetry breaking in ferroelectric materials is essential to tuning their functional properties. While optical second harmonic generation (SHG) has long been utilized in ferroelectric studies, its capability for probing complex polar materials has yet to be fully realized. Here, we develop a SHG spectral imaging method implemented on a home-designed laser-scanning SHG microscope, and demonstrate its application for a model system of (K, Na)NbO₃ single crystals. Supervised model fitting analysis produces comprehensive information about the polarization vector orientations and relative fractions of constituent domain variants as well as their thermal evolution across the polymorphic phase transitions. Multiple domains and phases are clearly delineated at different temperatures, suggesting the phase competitions in (K, Na)NbO₃. Besides, we show that unsupervised matrix decomposition analysis can quickly and faithfully reveal domain configurations without a priori knowledge about specific material systems. The SHG spectral imaging method can be readily extended to other ferroelectric materials with potentials to be further enhanced.