If you plan on using the Arctic Silver thermal compound under the LED and the regular epoxy around the LED to secure it, that should work fine. In fact, that should also give you the maximum thermal conductivity. The various Arctic xx thermal compounds have better thermal conductivity than the Arctic xx thermal epoxies.
Mixing the AS5 compound into regular epoxy also will work. The general advice is to mix the two in a 1:1 weight ratio. The trick is knowing what the densities of AS5 vs epoxy are. You can calculate AS5 density from this statement from the Arctic web site: At a layer 0.003" thick, the 3.5 gram tube will cover approximately 16 square inches. A Google search will give you the density for a typical epoxy. Knowing the densities, you then mix the appropriate volume ratios to give you a 1:1 weight ratio. For example, if AS5 is 3X as dense as epoxy, then mix a 1:3 volume ratio of AS5 to epoxy to get the desired 1:1 weight ratio.
If you are looking for a cheap way to make thermal glue, you can mix aluminum nitride particles with regular epoxy. If the AlN comprises about 2/3 of the total volume, you should get thermal conductivity comparable to Arctic Silver epoxy.