The coupling strengthening principle of the double physical effect of plasma shock-cavitation was proposed, and the rationality of the cavitation effect in pulsed laser shock treatment under liquid-confined conditions needs to be confirmed urgently. The XRD testing method and 304 stainless steel, which is easy to obtain diffraction peaks, were selected to quantitatively detect and characterize the residual stress distribution in the action area of a single pulse laser beam. The test results and literature analysis show that the different process conditions of laser shock processing bring about different strength matching of the two stress effects of plasma shock and cavitation, and the main source of stress effect of femtosecond laser shock without coating is the cavitation effect. The actual effects of the laser pulse width and other process parameters such as the absorption layer and the constraint layer affect or determine the material modification principle of the pulsed laser surface treatment.