He thought it was an ordinary magic stone, chap 6 Rolf said he checked, quote "Checked it with my Appraisal skills turned out to be an ordinary stone" pretty dumb but yeah that how he didn't know. Also he said it "only reacted like a magic stone" so assuming he has tried to identify the stone but it didn't have an indication that it could be the resurrection stone. Tbf the stone probably reacts after a person has died(I have my qualms with how this stone work). And for how he got it. we do not know much about Rolf as a character, so he may have already had the stone, may have him picked it up on one of his many adventures to defeat the demon king. Very limited as it is a 6 chapter manga would be nice if was longer ig anyway, sorry for the long text, hope this helps a bit, even if it doesn't. Sorry

he just conveniently has the stone? And there is no context or background on how he got it? sigh