So, I've never actually played a shooter game before (I tend to play RPGs) so I don't actually know much about how they play. Does anyone have any advice for these kinds of games?
As most people have said, the single-play portion of the game will help you a lot when it comes to controls, introducing you to the weapons, how the game works, as well as some movement. Movement is very important in shooters. There are some classes/weapons where you don't want to move around while trying to aim (such as a sniper) because it could ruin your shot. In Splatoon it might not be that way because of how the weapons and aiming works, at least if you're using the gamepad.
Honestly, it does pretty much come down to pratice. You'll gain more experience as you play, but a couple of tips I can give you is to always be aware of your surroundings. You need to have map awareness so you know where you're going, what escape routes will be available to you and any possible ways to flank the enemy. Movement is always key to survival. If you're standing still at any point, you're making yourself an easy target. Try to strafe while shooting, but don't be too predictable! If you just keep strafing in the same direction, your opponent will know where you're going, and you may not be paying attention to what's around you if you're focusing on who you're fighting. You don't want to walk into a wall when you're in a fight. Mix it up a little. Also, you'll always want to get the drop on your opponent so try not to waste the element of surprise. If you catch them off-guard, they're at a huge disadvantage, which can also apply to you if you're not careful.
Single-player won't teach you everything you need to know, mainly because actual players will play differently to any AI characters. If you're confident that you've got the hang of things, give multiplayer a try. It's not going to be a super competitive game in your first bunch of matches, and you'll get the hang of playing against other people in no time. I'll also suggest trying to assess a situation before you do engage in a fight. Don't blindly rush into something thinking you've got the upper hand, because there could always be another enemy just outside of your view. Leading on from that, I will say that you shouldn't be afraid to retreat from a fight if it starts going badly, especially in Splatoon! If you're alive, your team can leap over to you and help you fix the tricky situation. If you let yourself die, your team loses a chance to jump in and help and you'll be setting your team back as a whole if that happens.
Lastly, the most important thing to remember is to have fun. If you're not enjoying yourself at any point, just take a step back and relax. I find that when I get annoyed, I lose a lot of concentration and skill in those situations. When I'm having fun, I tend to focus a little better and even perform better, which leaves me enjoying the game because I know I'm doing my best and having a blast while doing so.