That would significantly change the meaning, at least in American English. Instead of "rule" being the noun and "headphones" the adjective, "headphones" could then easily be taken as the noun and "rule" the adjective with the change you propose.
"The Headphones Rule" more obviously means "a regulation pertaining to the usage of headphones".
"Headphones Rule" is very common slang meaning "headphones are superior".
"The Headphones Rule" more obviously means "a regulation pertaining to the usage of headphones".
"Headphones Rule" is very common slang meaning "headphones are superior".