From within ISE13.3's Project Manager, having a VHDL project:
Select the "Design" tab
In the Hierarchy pane (upper area) select the top-level unit of your
design
In the Processes pane (lower area), expand "Synthesize - XST" and
double-click on "Generate Post Synthesis Simulation Model"
This generates a folder within your project named netgen/synthesis and
within this folder, there is a file named <top>_synthesis, where <top> is
the name of your project's top level VHDL file.
This file must be compiled with ModelSim, together with your testbench.
I'm not sure what is necessary to launch ModelSim directly from ISE,
because I'm always using separate scripts for ModelSim.
regards
Guenter