First, most states, if not all, require a hunter safety course before you can get a hunting license. Most hunter safety courses will require you to show proficiency at the end of the course. They can tell you the laws of your state regarding the purchase of a rifle as well as safe places to shoot. This is only a start.
Before actually hunting, making sure your weapon is unloaded, practice at home time and time again, bringing the gun to bear on imaginary targets. With the gun in carry position, focus at a spot on the wall, close your eyes and bring the gun to shooting position, then open eyes and see if the sights are aligned and how close to the actual target you are. Practice until it becomes second nature. Next, go out in the field, without your gun, look for targets (stumps, rocks, branches, anything) and as you bring your imaginary gun to bear, condition yourself to look at the background behind your target. Most hunting accidents, other than self inflicted, happen when a hunter misses a real target and the bullet passes on and hits someone beyond. This quick scan should be at least 30 degrees on both sides of your target.
For most, hunting is a family tradition thing. We learn the basics very young from fathers and grandfathers, practicing the above measures with our toy guns. I strongly suggest you find someone willing to actually take you in the field your first few times hunting.
And my last suggestion, don't be in a hurry to make that first kill. A missed opportunity is much better than having to live with an accident.