>>1614083Like I said, you need to have both your nodes and handles be parallel on each side (Refer to image). Obviously, with hands there are generally more curves for the knuckles and with how easy the fingers flex, the shapes can get more complex and use more nodes. With that, the hardest part you are going to have is knowing how many nodes you need and where to place them. A good way to start is to draw just the end points for a line, and then just move the lines to places where a node makes sense. Do try to keep them to a minimum though. Derpy knows this better and has used Inkscape more than I have, so he might be able to explain it better later...
Once you get the nodes and handles parallel, then you want to pick what kind of thickness you want different parts of the body to be. Some opt for hair as the thinnest, then skin, then clothes, while some do the exact opposite. It doesn't really matter which you do, so long as you feel comfortable doing it and keep it consistent.
As for Illustrator and Inkscape, they are different in how you use the tools, but the ending result is the same. You just need to understand how the tools work in either program and get comfortable with them.