Angular distribution relates to the direction of propagation of radiative energy. Light coming from a non-punctual source comes in a range of directions.
If you use the ray approximation of light like in the Monte Carlo ray-tracing method, the angle of the rays coming from the source are computed from an angular deviation probability distribution compared with the vector normal to the surface at the point of emission of the ray.
For solar data, a common first order asumption is the "pillbox" sunshape distribution where the intensity probability distribution is uniform over the angular range of the sun and zero after that. After that you can check the Buie sunshape model that gives better approximation of the sunshape profile (http://www.sciencedirect.com/science/article/pii/S0038092X03001257).
Spatial distribution relates to the starting position of the emitted rays. To perform meaningful statistics with the Monte Carlo method you need to have spatially uniform repartition of the rays starting position, otherwise you bias the statistics.
The starting positions of these rays are computed using a distinct probability distribution able to uniformly distribute them over the surface of emission.
You can certainly use Monte Carlo simulation to estimate the individual values or relationship between the two parameters. In order to do so, you'll first need to come up with some starting estimates for both, and then you use MC simulation to come up with multiple (thousands) of randomly drawn estimates. Thus, you'll need to first come up with the variables and assume their distribution.