The enhancement of rice quality stands as a pivotal focus in crop breeding research, with spectral analysis-based non-destructive quality assessment emerging as a widely adopted tool in agriculture. A prevalent trend in this field prioritizes the assessment of effectiveness of individual spectral technologies while overlooking the influence of sample type on spectral quality testing outcomes. Thus, the present study employed Microscopic Hyperspectral Imaging, Raman, and Laser-Induced Breakdown Spectroscopy (LIBS) to acquire spectral data from paddy rice, brown rice, polished rice, and rice flour. The data were then modeled and analyzed with respect to the amylopectin and protein contents of the rice samples via regression methods. Correlation analysis revealed varying degrees of correlation, both positive and negative, among the three spectral techniques and the analytes of interest. LIBS and Raman spectroscopy demonstrated stronger correlations with the analytes compared to microscopic hyperspectral imaging. Based on the selected correlation variables, feature screening and regression modeling were conducted. The modeling results indicated that microscopic hyperspectral data modeling yielded the lowest coefficient of determination of R² = 0.2, followed by Raman data modeling result was higher than it, which was about 0.5. The modeling effect of polished rice is the best. LIBS data modeling performed best, with a coefficient of determination of 0.6. The influence of different sample types on the modeling results was less than that of Raman spectroscopy, and modeling results of grains were better. The feature matching analysis of Raman and libs spectroscopy techniques showed that there were spectral variables that could match amylopectin and protein in the features obtained by multiple modeling statistics, but some modeling variables failed to match. LIBS matched more variables than Raman. These findings provide valuable insights into the application effectiveness of different spectral techniques in detecting rice contents across diverse sample types.