I'm betting if you PM any one in particular and they were under the belief that another could better assist, that they would either join them to the PM or refer you to them.
Even when I've been on the receiving end of a mod-stick (having broken a rule or done something wrong) I've had extremely pleasant experiences with moderators here. If I need to reach out, my selection process usually comes down to checking the "Staff Online Now" box right under my username on the main page, and sending them a PM.