The front wheels will always "center" on the road, so that the toe is equally divided between both.
To compensate for your cocked wheel you need to shorten one tie rod and lengthen the other. An alignment shop should be able to do this, or if you want to do it yourself, on a level surface, straighten the steering wheel, then sight down the side of the tires and adjust the tie rods so the front wheels are straight to just a hair of toe in. Now set the toe in to about 1/16" and sight down the sides of the tires to see that they have an equal hint of toe in. Recheck that the steering wheel is straight as you adjust the tie rods.
When you think you have it, take it for a test drive, and if it's still cocked you'll have to tweak the tie rods some more. Just make sure that when the steering wheel is straight, you still have the proper range of toe-in.