Noninvasive dental diagnostics is a growing discipline since it has been established that early detection and quantification of tooth mineral loss can reverse caries lesions in their incipient state. A theoretical coupled diffuse photon density and thermal-wave model was developed and applied to photothermal radiometric frequency responses, fitted to experimental data using a multiparameter simplex downhill minimization algorithm for the extraction of optothermophysical properties from artificially demineralized human enamel. The aim of this study was to evaluate the reliability and robustness of the advanced fitting algorithm. The results showed a select group of optical and thermal transport parameters and thicknesses were reliably extracted from the computational fitting algorithm. Theoretically derived thicknesses were accurately predicted, within about 20% error, while the estimated error in the optical and thermal property evaluation was within the values determined from early studies using destructive analyses. The high fidelity of the theoretical model illustrates its efficacy, reliability, and applicability toward the nondestructive characterization of depthwise inhomogeneous sound enamel and complex enamel caries lesions.