If you want players to know the rules backwards and forwards, first let the players have a cheatsheet. Every single "official" cheatsheet I've found for any particular ruleset has either too much info on stuff I don't care about (I play the fighter, and the spell rules are irrelevant), or not enough detail about what I need (I play a fighter, and there aren't rules on grappling, AoO, etc). Encourage the players to make their own (and put book/page number references), and encourage them to change their sheets as they learn rules and don't need specific sections. Sure, my first session I'll need to know how to do basic attacks, but after a few sessions, that real estate is better used on combat maneuvers, or other "advanced" stuff. If players keep taking off stuff they know to put on rules they don't know, then they are learning the system.
Second, allow all the books, etc at the table, but house-rule that once it is a player's turn, he gets 10 seconds to state his action, or ask a question. After you answer any question(s), restart the 10 seconds. If a player does not know their action, they "delay" or "fight defensively while they survey their options" for a round. Apply whatever bonus would be applied (it's +2 to AC in Pathfinder). On the flip-side, let them look up whatever they want between turns (I know some GMs that hate when players touch rulebooks, since they say it breaks immersion). Also, during their turn they can only use a rulebook if it is open to the relevant page, or their cheatsheet for reference.
Third, if you don't know how to do it, you can't do it. If a player doesn't look up the rules on how to do a diving back-flip while cartwheeling around a bad guy (to avoid AoO), while charging another bad guy, then he doesn't get the benefit of that maneuver. He can move/attack with "normal" attacks, but that's it.
Fourth, decide whether computers/internet devices are allowed at the table. If you allow them, someone will go to CNN.com (or similar site) and get distracted, if you disallow such devices, then someone will not know how to look up what they want to do and won't be able to do it. Feelings may get hurt as a result. If computers are allowed, they should (theoretically) replace the chin-high stack of open books.