diariamente is an adverb and means every day.
eu tomo banho diariamente. (I take a bath every day)
eu estudo diariamente. (I study every day)
diário is an adjective and means daily
notícias diárias (daily news)
correio diário (daily mail)
You should use each being aware of the usage of adverbs and adjectives
(adverbs aren't necessary for the general understanding of a phrase; they are just accessories)
ex: Eu estudo. (that can be understood just by itself right?)
ex: Eu estudo diariamente. (now, we call diariamente a temporal adverb wich indicates when or for how long the action is done.)
(adjectives give attributes, qualities to a noun.)
ex. Ele se exercita. (here, exercita is a verb.)
ex. Ele pratica exercícios diários. (Now, it is a noun with the attribute "daily")
there's also the noun Diário, wich means diary (nikki) or a daily newspaper
diariamente and diário mean the same thing, you just need to be careful about the grammar in order to use them correctly.