So it looks like you have one with Y axis, smart, do it right or don't do it. Machines without Y axis have limited use and people often regret not stepping up another notch.
Now, you have to separate turning and milling, although it is possible to turn hexagon by using C axis and turning tool, same is not true for arbitrary shapes. You turn round shapes concentric with Z axis and you mill everything else.
For most millwork on bar face, use tool in axial orientation, parallel with Z axis.
For most work on OD of the part,use tool in radial orientation, tool perpendicular to Z axis.
I say "most" in both cases because there are times when that will not be the only option in either case.
As far as learning the basics, there are training materials up there at the top of the forum page, dig around.
Also, if you search words related to mil-turn work you will dig up many posts with practical examples of projects that include assortment of tool paths, I have my fingers in many of them because that's what I do every day.
Rotary tool path is no longer free so that cuts you off in some cases where that was the key choice but if you find it useful, let your wallet speak.
