When an experienced user (on or from any Stack Exchange site), asks a question on a particular Stack Exchange site, I think it is reasonable to assume that they are familiar with about 90% of the Tour for that site because only a small part of the Tour supports per-site customization.
Consequently, suggesting users review the Tour as part of learning about the site and its protocols is something that I normally reserve for users with much less than a reputation of 101 i.e. usually only those with a reputation at or near 1.
However, when an experienced user is asking questions or making comments that contradict any guidelines in the Tour that the community has deemed important enough to place in that very limited screen real estate, I think it is reasonable to alert them to where we have tried to provide that information for them to read and note when they join the site.
A common comment I might make after coming across a question from an experienced user that contains multiple questions is:
As per the Tour there should be only one question asked per question.
This message has not been softened by writing several flowery sentences or looking up the Meta discussion about why that is the case, because doing so takes much more of my volunteered time. In any event, I am making that comment to an experienced user, so I think it is reasonable to assume that they will be familiar with the protocols of focused Q&A like "no chit chat" and realize that I am focussing on the question content and not their feelings. My perception is that this is understood by most of them, who then view the Tour and/or usually ask one question per question from then on.