When releasing a skunk from a live trap, it's best not to stick your face in the trap.
As much as we love wildlife, there are parts of it we don't want around us. Skunks are generally not welcome in residential areas. If you live in a city, you're generally stuck trapping the critter and relocating it since most municipalities frown upon discharging firearms within city limits. Just make sure you don't follow this guy's example.
As I was searching for skunk trapping advice on YouTube, I came across several videos showing what not to do. I thought this one was particularly amusing, as the guy actually sticks his face in the end of the trap and tries reaching in for the skunk. I'm sorry, but common sense should tell you to keep a little more distance.
If you have a skunk problem, there are special traps that look like PVC tubes that prevent it from spraying once trapped. These traps can run upwards of $100. For an easier and cheaper method of catching a skunk without getting sprayed, place your trap in a dog food bag cutting a slit for the handle. This will make sure the skunk spray doesn't hit you once the varmint is trapped.
Now, as far as releasing it without getting sprayed, that's another story. The best advice I can give is just don't do what the guy in the video does! Do you think his girlfriend let him get back in the car to ride home?