No, there is not an obvious way to use Deval with Simulink output. However, you can use "Configuration Parameters"-->"Data Import/Export" to do the similar things that you can do with Deval. For instance, the "refine factor" allows a smoother output without reducing the step size or restricting the solver step size. Polynomial interpolation is used to interpolate in between time steps. The polynomial interpolation has the same order of accuracy as the solver. You can also request output at specific times with "produce additional output" or "Produce specificied output only" as shown below.