Since there will be times when they are out of fairies and potions, here are my headcanons for how much training and/or experience the LU boys have with first-aid and other sorts of medical treatment.
In order from highest to lowest:
Sky and Warriors: These two have, at some point their lives, been sat down in a room with other people with an instructor telling them "Sometimes people will be hurt and it will be your job to fix them, here's how." Between the two, I think Sky got more in-depth instruction (a Knight of Skyloft is basically a lifeguard), but Wars has gotten more practical experience. Either one is a good man to have on hand if you have a non-fatal arrow in your torso.
Time and Twilight: These are the two the fandom is really sleeping on when it comes to battlefield medicine, and here's why. What do they do when they're not hero-ing across time and space? They're ranchers. As in...they raise livestock. Livestock has a bad habit of getting itself injured and/or sick, so any successful rancher picks up some basics of veterinary medicine, and here's the really neat part...veterinary medicine is often generalizable to human patients. Disinfecting wounds, splinting bones, and diagnosing minor illnesses works about the same no matter what kind of mammal you're dealing with.
Legend: Experience, baby. With at least five adventures under his belt, he'll have absorbed a fair amount of practical knowledge just from necessity. And his broad travels will have exposed him to multiple different bodies of knowledge from different cultures, which might patch a few gaps in what the rest of the Chain knows.
Wind: A specialist. In cases of water inhalation, sunburn, rope burn, incidental nausea, or any other ailment heavily associated with sea travel, he's your guy. Beyond that, he's still learning. Give him a break, he's only 13.
Wild: No one gets by in the wilderness without knowing how to patch up various cuts and scrapes and stabilize sprained joints. That said, his recklessness works against him here. He's the most likely to be walking around with a small stick broken off in his shoulder and thinking nothing of it, and if you have a small stick broken off in your shoulder he's certainly not going to point it out and ruin your afternoon.
Hyrule: A lot of fans like to make him the backup medic (or even the main medic) because of his Life spell, but I think it would have the opposite effect. Rulie did the standard "young hero learning basic first-aid through a combination of incidental tips from wise old men in caves and personal trial and error," but once he gained the ability to just heal himself magically, he started to rely on that and his skills atrophied.
Four: Like Wind, he's a specialist--he knows what to do for burns of all different severities (it was part of his forge training). Unlike Wind, he's fairly sheltered beyond that. Four is a city boy who hasn't done a whole lot of traveling in his adventures and his first instinct when someone is hurt is to call an actual doctor. He has the same grounding in first-aid as the rest of them, but his temperament sometimes betrays him in an emergency.
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