As long as the PvP SA relics stack as they currently do, I would recommend this spec (for PvE) instead:
You want the self heal from "Cool Under Pressure" to proc/refresh the power surge from the SA relics. I would also recommend taking 3/3 from "Independent Anarchy" and using the 2 piece PvP set bonus to really boost XS Freighter Flyby's damage. You can also stack the PvP set bonus, giving 2 extra ticks by using 2 Conqueror/Partisan Armorings with either 2 War Hero or 2 Battlemaster armorings.
I agree that the ~1.5 sec break before Aimed Shot comes off CD is a good time to use Vital Shot, but I don't think it should be that high on the priority list. It's really more of a filler ability - if for example that 1.5 sec window wasn't there, it would not be wise to use VS instead of AS as your priority list would currently suggest. Therefore, if you have enough energy when you reach that 1.5 sec window, go ahead and use VS, otherwise just use Flurry of Bolts.
Finally, I could not find any mention of "Smuggler's Luck" in this guide. It's basically a free crit on CB since it doesn't respect the GCD.