Just making sure you ask questions is good. I've noticed I tend to just answer their questions and evaluate them based on how they respond to me but if I ever see a pdoc again (I've sworn to myself I won't because I believe they've caused more harm than good for me) I'll be asking alot more questions.

For example:
Even if they mention side effects to a med I'll press them with more questions like how often they've prescribed it to their patients, what issues others have had with it, what might happen, when and how should I contact them if I believe I'm having side effects. Many pdocs don't seem to like the side effects conversation, I don't know if they assume everyone is a potential hypochondriac or what...

I'd also ask what happens if you are not having any sort of emergency but are not doing well and would like a sooner appointment or if they cancel an appointment and become unavailable in a timely manner (say within 48 hrs m-f). I say this because my last pdoc had a personal crisis and just jumped ship. To make matters worse he didn't even communicate his crisis until I politely asked him why his availability had so dramatically changed overnight (to not available, canceling appointments, delaying for weeks making new one). I won't see a pdoc now that doesn't have a back up plan. Ask if they have a dr that covers them.

Go ahead and ask their impression of something you said, something that came up or for any type of clarification. You are placing trust in this person, working with them and it's kinda weird to tell a stranger personal stuff even if they are a pdoc. It can feel intimidating but it needn't be and ambiguity isn't necessary. Pdocs that act like their's is the word of God are not a "good fit" for most.

Also, if they want to put you on a med ask what your options are. I really liked it when my dr gave me a few options, told me his impressions of how each may work for me and then let me go home and consider my options before emailing him a reply.
Some pdocs are heavy prescribers and if you go to a clinic type setting (low income, not private practice) they tend to prescribe higher dosages. You can ask how they approach starting a med and ask to taper up slowly. I had one pdoc tell me he prefered higher dosages because he thought they saturated the brain and would produce better results. I'm not ok with the saturation idea, I ask for the lowest possible dose and to taper up slowly.

Finally, you could encounter a weirdo that tries to pressure you with the notion you "should" be on meds without even seeing a therapist. If you feel in a tight spot where you feel like they might not give you a referral to a therapist unless you let them put you on or make changes to meds go ahead and pretend you're fine with whatever they say. This is a worst case scenario and I doubt it will happen but it happened once to me. Instead of letting their ego have control over you accessing help just play along.

You're likely to have a fairly comfortable experience with a decent person, I gave you worst case scenarios.
Good luck!