Am I remembering right here? Shoot a skunk in the body, no spray. Shoot him in the brain, spray. On the TAG a guy was complaining about a head shot skunk where it sprayed and almost caused him to sleep in the barn.

a properly placed head shot (e.g. Brain) has never failed me.

I had a skunk in a trap and I shot it with a .22 and it sprayed. Now when I trap one, I call animal control. They even had a couple of women that might handle the situation. They have a needle on a stick about 3 feet long. They just walk up to the trap and place the needle against the skunk and it leans into it. That shot puts skunk to sleep. They change to another shot that euthanizes the skunk. Put on rubber glove get skunk and put in plastic trash bag and they are on their way. Takes 5 minutes thereabouts.

I still don't want the skunk to spray because I shot him in a nerve center. Airgun or otherwise.

One other rather bit of obvious advice...stand up wind!

I have shot hundreds of skunks they all spray.

The best way is the syringe method go to you local farm supply by some.

epoxy the plunger into some pcv pipe one can shorten or lengthen just by using connectors.

fill the syringe with acetone slowly inject the skunk dead shortly no fuss no mess.

As usuall, I agree with p dog shooter ( I sometimes wonder if we share the same brain! )
I once had a skunk get in under the porch of the house. It kept pissing and stinking until I'd had enough.
I set a spring trap under there, with a rope tied to the pic-nic table. I woke up in the night when it was caught and sprayed. Grabbed a 22 pistol and flashlight. I took the end of the rope and took off running up the field. Stopped and put the light on it to shoot, and it regained it's feet and lifted it's tail. Off and running again. After bouncing it around to the other end of the field I could shoot it!
Now I set a box trap, toss an old blanket over the cage, take it off somewhere to let out and shoot it then.