Soybean seed purity is a critical factor in agricultural products, standardization of seed quality, and food processing. In this study, laser-induced breakdown spectroscopy (LIBS) as an effective technology was successfully used to identify ten varieties of soybean seeds. We improved the traditional sample preparation scheme for LIBS. Instead of grinding and squashing, we propose a time-efficient method by pressing soybean seeds into rubber sand filled with culture plates through a ruler to ensure a relatively uniform surface height. In our experimental scheme, three LIBS spectra were finally collected for each soybean seed. A majority vote based on three spectra was applied as the final decision judging the attribution of a single soybean seed. The results showed that the support vector machine (SVM) obtained the optimal identification accuracy of 90% in the prediction set. In addition, PCA-ResNet (propagation coefficient adaptive ResNet) and PCSA-ResNet (propagation coefficient synchronous adaptive ResNet) were designed based on typical ResNet structure by changing the way of self-adaption of propagation coefficients. Combined with a new form of input data called spectral matrix, PCSA-ResNet obtained the optimal performance with the discriminate accuracy of 91.75% in the prediction set. T-distributed stochastic neighbor embedding (t-SNE) was used to visualize the clustering process of the extracted features by PCSA-ResNet. For the interpretation of the good performance of PCSA-ResNet coupled with the spectral matrix, saliency maps were further applied to visually show the pixel positions of the spectral matrix that had a significant influence on the discrimination results, indicating that the content and proportion of elements in soybean seeds could reflect the variety differences.