I understand that modifiers will create a smooth surface on cylinders for still works and animation but how do I achieve this for 3D printing? Also, do I need to be mindful of making a cylinder with more vertexes (64 instead of 32) to achieve this end?
You can have hundreds of vertices to get a smooth cylinder, if u like. There is no limit. The slicing program you use might get slow if you have many verts(>100k on my machine), but it will work. Modifiers only change the look of the object unless you apply them, this option is in the down pointing angle to the right on the modifiers. To add many verts to a newly created cylinder will give you a similar result to applying a modifier. Look at the mesh in edit mode to see what the applying of the modifier did. The resolution of most 3d printers are such that a round object will be perfectly round if the mesh in blender has enough resolution.