First and for most I would avoid using the express VIs. Learn the DAQ primitives and use those. Express VIs tend to reinitialize the DAQ task every time and this will cause a performance issue. I can't really comment on whether your percentages will always equal 100 or how your third party library will deal with that. When working with floating point values you should never rely on testing equality but rather test using a tolerance. Because as you stated, digits of precision can come into play.
Regarding some basic tips for clean code, here are a few basic guidelines:
Keep your wire flow going left to right
Avoid wire bends as much as you can
Don't run wires backwards
Keep your block diagram small, it should not be larger than a single display. Smaller is not bad since it will accommodate laptops.
Use subVIs. Especially if you find yourself copying and pasting code on your diagram.
Label things
Take some time to learn some of the various architectures (basic: state machines and producer/consumer; advanced: queued message handler, actor framework)
There is an older book by Peter Blume but it is still very informative: LabVIEW Style Book