The start and end points of a linear gradient are specified in points relative to the whole size of the layer, with (0,0) at the top left and (1,1) at the bottom right.
Therefore, to make a linear gradient at an angle, you simply need to set the start and end points appropriately. For example, If you used (0,0) and (1,1) as the start and end points, the gradient would run from the top left to the bottom right, at a 45 degree angle.
Working out the specific start and end points for your needs is therefore just a matter of trigonometry.