In order to avoid the spectral signal instability and low detection accuracy originating from “transient plasma” produced by laser-induced breakdown (LIBS) technology, the LIBS system based on three-dimensional scaffold was developed to optimize the optical fiber detection position. The spectral signal quality of samples with different contents of KCl additives (0%–100%) at 20–280 °C was analyzed. The double spectral line internal standard model of Cd and Pb elements in sediment was established. The experimental results show that the signal-to-noise ratio of Cd and Al in the sediment with 15% KCl additive at 180 °C is 1.78 and 1.39 times higher than that without additive at room temperature. The R2 of the calibration model for Cd and Pb in sediment with the double enhancement method increased from 0.938 08 and 0.948 80 to 0.963 41 and 0.952 61. The spectral line integral area bispectral line internal scale model R2 is improved to 0.990 34 and 0.988 83. The results showed that the sample heating combined with KCl additive could improve the quality of the spectral signal and increase the detection sensitivity.