The suffix -an -en is always added to the verbs and gives the structure 'relative in active form' to the verb.
For example:
Giden adam - The man who goes/is going etc.
Or only Giden - The one who goes/is going etc.
So olan means ... Which happens/is/becomes etc. (Olmak means to be, to become, to happen etc.)
So değerli olan can mean:
Değerli olan ev: the house which is valuable.
Değerli olan söz: the remark/the word which is worthy
Değerli olan budur: this is what is worthy / this is the one which is worthy.
But when you use only değerli, that means you use adjective.
Şuradaki ev değerlidir - that house/the house there is valuable.
Değerli bir insandır - he is a worthy person. Etc.
So when you see a verb which ends with -an -en, remember there is a relative clause in it.
As a result the answer of your question is: one is relative clause, but the other is adjective.