Firstly, thanks for asking a good question. I like this forum but I am so fed up with people asking things such as "teach me how to build the best antenna in the world! NOW!".
As for the answer: I don't really know. I use HFSS on a daily basis but never needed the layered impedance boundary.
From what I see, it is just an impedance boundary but it automates the process for you: When you put in the layers in the dialog box and hit calculate it assigns that calculated impedance to the surface. So try different values and hit calculate and see if you are getting an impedance in the expected range.
Also I have a question, what if you just defined the surface in 3d? I know it would take more resources but may be you could compare a small 3d sample to the impedance surface and see if the results are the same.
Good luck, I am interested in the solution to this.