I was looking for the first episode where Niles asks Daphne what scent she is wearing and she tells him Cherry Bark and Almonds.

I know it is in Season 6 episode 15 To Tell The Truth, but it is when Donny and Daphne are together. It's mentioned in an earlier episode, but I can't find it.

Can you help?

Is S06 E15 the first mention of Cherry Bark and Almonds???

I think it's the only mention of that particular combination. There's another episode where Freddie says Daphne's hair smells like strawberries and Niles corrects him and says something like 'it smells like peach blossoms and vanilla, at least it does from here.' I'm not sure if that's his exact phrasing-- it probably isn't-- but I know it wasn't cherry bark and almonds that he said that time, he said something about peaches. And I think those are the only two times he attached a description to the way her hair smells. I don't remember which Freddie episode that was-- maybe the "you can fool them but you can't fool me--I'm on to you little man!" one.
The only other time we got any indication of what her hair might smell like is in First Date when she talked about spraying her perfume Obsession on her brush and brushing it through her hair..."isn't that silly? As if anyone is going to smell my hair!"
I have noticed before that it's never been the same thing that is used to describe how her hair smells. lol

I think it's the only mention of that particular combination. There's another episode where Freddie says Daphne's hair smells like strawberries and Niles corrects him and says something like 'it smells like peach blossoms and vanilla, at least it does from here.' I'm not sure if that's his exact phrasing-- it probably isn't-- but I know it wasn't cherry bark and almonds that he said that time, he said something about peaches. And I think those are the only two times he attached a description to the way her hair smells. I don't remember which Freddie episode that was-- maybe the "you can fool them but you can't fool me--I'm on to you little man!" one.
The only other time we got any indication of what her hair might smell like is in First Date when she talked about spraying her perfume Obsession on her brush and brushing it through her hair..."isn't that silly? As if anyone is going to smell my hair!"
I have noticed before that it's never been the same thing that is used to describe how her hair smells. lol

Ha! I love that episode with Frederick and how jealous Niles is of him! And then toward the end of the series when Frederick is there again, Niles is like "I got her and you can't have her!" That is hilarious!