A な-adjective takes な when it goes in front of a noun to describe it: しずか静か "quiet" becomes しずか静かなへや部屋 "a quiet room". Without な the two words don't join.
An い-adjective needs nothing in between: おおきい大きいいえ家, "a big house".
な only appears before a noun. At the end of a sentence the な-adjective takes です or だ instead.
A few な-adjectives end in the sound い, so they look like い-adjectives: きれい, ゆうめい有名, きらい嫌い. They still take な before a noun, and the い is part of the word, not an ending.