For MgCl2.6H2O, the solubility at 20°C is 235g/100mL. How much solvent (water) do I need to use to achieve that solubility? Is it 100mL of water or do I reduce it with the amount of water in the hydrated MgCl2?

If you are making a solution in which you want the solution to be MgCl2.6H2O, then 235 g/100 mL is the correct value.