Canopy chlorophyll content (CCC) is an important indicator for crop-growth monitoring and crop productivity estimation. The hybrid method, involving the PROSAIL radiative transfer model and machine learning algorithms, has been widely applied for crop CCC retrieval. However, PROSAIL’s homogeneous canopy hypothesis limits the ability to use the PROSAIL-based CCC estimation across different crops with a row structure. In addition to leaf area index (LAI), average leaf angle (ALA) is the most important canopy structure factor in the PROSAIL model. Under the same LAI, adjustment of the ALA can make a PROSAIL simulation obtain the same canopy gap as the heterogeneous canopy at a specific observation angle. Therefore, parameterization of an adjusted ALA (ALAadj) is an optimal choice to make the PROSAIL model suitable for specific row-planted crops. This paper attempted to improve PROSAIL-based CCC retrieval for different crops, using a random forest algorithm, by introducing the prior knowledge of crop-specific ALAadj. Based on the field reflectance spectrum at nadir, leaf area index, and leaf chlorophyll content, parameterization of the ALAadj in the PROSAIL model for wheat and soybean was carried out. An algorithm integrating the random forest and PROSAIL simulations with prior ALAadj information was developed for wheat and soybean CCC retrieval. Ground-measured CCC measurements were used to validate the CCC retrieved from canopy spectra. The results showed that the ALAadj values (62 degrees for wheat; 45 degrees for soybean) that were parameterized for the PROSAIL model demonstrated good discrimination between the two crops. The proposed algorithm improved the CCC retrieval accuracy for wheat and soybean, regardless of whether continuous visible to near-infrared spectra with 50 bands (RMSE from 39.9 to 32.9 μg cm−2; R2 from 0.67 to 0.76) or discrete spectra with 13 bands (RMSE from 43.9 to 33.7 μg cm−2; R2 from 0.63 to 0.74) and nine bands (RMSE from 45.1 to 37.0 μg cm−2; R2 from 0.61 to 0.71) were used. The proposed hybrid algorithm, based on PROSAIL simulations with ALAadj, has the potential for satellite-based CCC estimation across different crop types, and it also has a good reference value for the retrieval of other crop parameters.