A variety of spectral vegetation indices (SVIs) have been constructed to monitor crop water stress. However, their abilities to reflect dynamic canopy water content (CWC) and vegetation water content (VWC) during the growing season have not been concurrently examined, and the underlying mechanisms remain unclear, especially in relation to soil drying. In this study, a field experiment was conducted and designed with various irrigation regimes applied during two consecutive growing seasons of maize. The results showed that CWC, VWC, and the SVIs exhibited obvious trends of first increasing and then decreasing within a growing season. In addition, VWC was allometrically related to CWC across the two growing seasons. A linear relationship between the five SVIs and CWC occurred within a certain CWC range (0.01–0.41 kg m−2), while the relationship between these SVIs and VWC was nonlinear. Furthermore, the five SVIs indicated critical values for VWC, and these values were 1.12 and 1.15 kg m−2 for the water index (WI) and normalized difference water index (NDWI), respectively; however, the normalized difference infrared index (NDII), normalized difference vegetation index (NDVI), and optimal soil-adjusted vegetation index (OSAVI) had the same critical value of 0.55 kg m−2. Therefore, in comparison to the NDII, NDVI, and OSAVI, the WI and NDWI better reflected the crop water content based on their sensitives to CWC and VWC. Moreover, CWC was the most important direct biotic driver of the dynamics of SVIs, while leaf area index (LAI) was the most important indirect biotic driver. VWC was a critical indirect regulator of WI, NDWI, NDII, and OSAVI dynamics, whereas vegetation dry mass (VDM) was the critical indirect regulator of NDVI dynamics. These findings may provide additional information for estimating agricultural drought and insights on the impact mechanism of soil water deficits on SVIs.