Tim, this is in general difficult (as the suggestions show). What I would do in/with Magma is
- compute an explicit co-cycle parametrizing your central simple algebra. For this to work, you need a matrix representation over a number field that is normal over the centre of the algebra. (Basically compute the Galois action as conjugating matrices)
- from the co-cycle you can compute the Schur-indices as the exponent in the Brauer group (either globally or locally)
- comparing dimensions you should be able to see if you have a division algebra (skew-field) or not.
The MeatAxe approach can also be useful - Allan Steel developed this systematically further. However, in difficult cases, currently, one needs to revert to the Galois cohomology as above.
PS.: an improvement, while using the same core idea is to compute a maximal order of the algebra. The discriminant gives then enough information to derive the Schur indices, thus avoiding the Galois cohomology.