Under the same nitrogen fertilizer and cultivation conditions, the nutrients of rice are strongly affected during the processing of brown rice to polished rice, especially in special rice varieties. In this study, twenty-two amino acids in brown and polished rice of two purple rice varieties were quantified using targeted metabolomics, and the relationships among the main nutrients, mineral elements and metabolites were analysed. The results showed that the amino acid levels in YZN1_H (polished rice of Yangzinuo No. 1) and YZN2_H (polished rice of Yangzinuo No. 2) decreased to different degrees compared with those in YZN1_B (brown rice of Yangzinuo No. 1) and YZN2_B (brown rice of Yangzinuo No. 2). Citric acid is closely associated with amino acids. The total sugar (TS), ATP, and soluble dietary fiber (SDF) levels in YZN1_B decreased by 9.37%, 53.85%, and 75.71%, respectively, compared with those in YZN1_H. The TS, ATP, and SDF levels in YZN2_B decreased significantly by 6.92%, 21.03%, and 76.78%, respectively, compared with those in YZN2_H. Citric acid was significantly negatively correlated with ATP and SDF but significantly positively correlated with carotenoids. The Se content in YZN1_H was significantly higher than that in YZN1_B by 87.02%. The Se content in YZN2_H was significantly higher than that in YZN2_B by 72.02%. Citric acid was significantly positively correlated with Fe, Mn, Ca, and Mg. Citric acid was identified as a candidate key metabolite that affects changes in the main nutrients in purple rice during processing.