LOL ...
I'm betting on you, Roxynoodle
I recommend you practice a few shots with the shotgun at 20 feet.
Get a cardboard box, plastic 5 gal bucket, slab of plywood... something you don't need anymore as a target... tape a rectangle about the size of skunk body on it as a target.. do something to designate which end is the head.
Place target in neighborhood of where yoou believe you are likely to see the skunk and do practice there... observe the pattern of shot. Use number 4 if you have to purchase shells. If you are using borrowed shells, number 2, 4, or 6 will do OK. I wouldn't go bigger or smaller.
Reason for practicing in neighborhood of where you anticipate seeing the skunk is that you will predetermine what area is OK to shoot into and what area has stuff you don't want shot up. Obviously, you will wait until the skunk is in a kill zone with nothing sensitive behind it.
Typical skunk behavior is to amble around and stop occasionally to look around. If possible, wait until it is stopped to take your shot. Most of the skunks I have seen do not RUN from a human that they observe but tend to move away at a medium clip, stopping occasionally. So, even if it sees you, typically there is time to move into a good/better shooting position or wait until it moves itself into a good location.
Suggestion... constrain your dog somehow... you don't want it as a distraction to you and/or the skunk while you are engaging the stinker!
Try several shots at different distances..... you will observe that the shot scatters out the further you are from the target. I repeat, a shotgun is lethal and will certainly do the trick. I like the idea of you getting some advice from the Deputy lady.
Somthing to focus on is keeping the butt of the gun to your shoulder, tight... OK, not terribly tight but just against the shoulder.... there will be a "kick" which drives the butt of the gun back as the pellets move forward. This is more surprising than painful ..... but if you have an inch of air between your shoulder and the butt of the gun, it sometimes can be a whallop. It's easy to avoid this, just something that often newbie shotgunners forget to do... keep the gun to your shoulder... makes for better aim, too.
Finally, this really isn't that hard... just a new experience for you... it'll be fun