This is all fascinating and informative, as I'm working on the Venezuela section of my website at the moment!
Just to add even more confusion, it appears that the entire thing was dropped and replaced in 2010 by the Orden Libertadores y Libertadoras de Venezuela in collar and 3 classes - and a quite different centrepiece to the badge, if a rather scruffy image in the Spanish version of Wikipedia is to be believed. No idea as to the design of the stars worn by Class 1 and Class 2, yet. The ribbon is yellow/blue/red with small white stars on the blue stripe.
I have found the law creating it, In Spanish of course, and am struggling my way through a translation (my Spanish is at the 'May I have a beer, please?' and 'Where is the bathroom?' level!). If anyone's good at Spanish I can send a copy over, she says hopefully...
I have found an image from earlier this year of a 100-year old musician called Juan Vicente Torrealba receiving the Class 1 of the order - you can see the stars on the sash and the star but it is not at all clear.