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I have been teaching in New York for ten years. It's great that you want to get a head start on your future. Volunteering is a great way to see how a classroom runs. However, to see a typical classroom it would have to be during school hours. There are programs where school partner with tutors. This will vary depending on where you live.
School pychologists get paid the same in New York as teachers do. There are pay increases for master's degrees, years of service,or becoming nationally certified. Again depending on whee you live, will determine how you are paid.
If you are interested in secondary education, you should try to find programs that are linked to your subject area (math, history, or literature) There are probably afterschool programs that you could work or volunteer for.
Teaching is a rewarding job. Good luck!
The best way to figure out teaching is the right fit for you is to volunteer at a school and work with the students. Also talk to the teachers. See what they like and dislike about there job. This should at least help you out before you start the process of school.