One way to assess the accuracy of the PLS method is by calculating the figures of merit (RMSEC, RMSEP, only is not enough), using REP or others according to the attached articles. Another very effective way is to compare the predicted data with the values found in a reference analytical technique for your method (i.e. HPLC)
Article Analytical Figures of Merit: From Univariate to Multiway Calibration
Article Determination of DEET, Icaridin, and IR3535 in insect repell...