As a new quantitative analysis method for heavy-metal elements in soil, the main function of the polarization resolution model is to filter out the disturbance of other elements on the spectral signal of target plasma. In order to quantify the mechanism of improving detection performance, the spectral transmittance of plasma intensity in the polarization-resolved optical path has been derived, and the relationship between the intensity of polarization-resolved laser-induced breakdown spectroscopy (PRLIBS) and the characteristic peak wavelength has been defined. Using the spectral data in the wavelength range of 424.50–429.24 nm as the characteristic signal, a quantitative analysis method for detection of the Cr element in soil has been developed. The improvement of spectral intensity stability at the characteristic peak of Cr I 425.7 was analyzed, and the mechanism of enhancing the detection accuracy was elucidated. Research has shown that, based on the polarization characteristics of Cr element plasma, PRLIBS is not affected by the matrix effects of soil and characterizes the amplitude conversion from the reference concentration of Cr element to the plasma spectral intensity. The spectral transmittance of plasma spectra depends not only on the characteristic peak wavelength and complex refractive index of heavy-metal elements but also on the measurement conditions such as spatial geometric angles and reflectivity of the transmission medium.