To have smooth lines, you have to do 2 things:
First, add a circle with a radius that is half the size of the current Line.Width in the currentx, currenty position each time you draw a line. This avoids that nasty looking line specially when the line is thick.
Second, a basic "anti-aliasing" method (if you don't know what that is, please check the image) which you get it by drawing first the line with the current paint color but with some transparency and 1 or 2 pixels thicker, then you draw the normal line on top of the "soft" line.
The results are surprisingly good, taking in consideration that App Inventor 2 is not really good for graphics.
If you tinker around with the colors, you can even achieve the "glow" effect that you wanted.
Please download the aia attached and see for yourself. In my example I use 2 passes for the anti aliasing, giving a very smooth line when you select the brush tool. If you select the pencil tool, the anti aliasing is skipped.

In this screen you see the "pencil" or normal way of drawing the lines, and the "brush" or anti aliased method with two passes
