Something that's unbuttoned isn't closed or fastened. Your unbuttoned sweater won't keep you very warm on a cold, windy day.
The adjective unbuttoned is what you need when you're talking about a piece of clothing with buttons that aren't fastened, like your unbuttoned wool coat or your unbuttoned, rolled-up shirt sleeves. You can also describe a relaxed or uninhibited person as unbuttoned: "My mom is kind of uptight today, but on the weekends she's way more unbuttoned."