How accurate are the results when I use optical modeling?
This is hard to tell, and it depends on many details. So there is no general answer to this question.
A good optical model should use the lowest possible number of parameters. If you have too many parameters in the model they may be correlated in a way that raising one parameter value and decreasing another leads to the same optical spectra. In this case the parameter values are more or less arbitrary, and the accuracy is very low.
The result of a parameter fit depends very much on the information contained in the measured data. If you want to determine a layer thickness, for example, you must have measured contributions of radiation which has seen the bottom of the layer, i.e. which has travelled through the layer at least once. If that is not the case in the spectral range that is accessible to you, you will never be able to get the thickness of the layer.