Is it cumulative? Should one start with those?
SpaceChem will introduce the idea of step-test-debug along with the modular piping (a bit); it has been a favorite for years. TIS-100 will introduce the assembler block programming, and is notable in that it manages to be fun!
Personally, I would start with SpaceChem, as it's fun right away and stays that way for a long time. It always feels like a game, while TIS-100 can feel a bit like work sometimes :P
Speaking of which, did you know that Zach himself never beat the last level of SpaceChem?