For the Transit Without Visa, you'll need to specifically tell the agent at the check-in counter of starting airport that you will be doing this, so they mark you in the passenger manifest correctly. On board the flight you'll get an arrival/departure card which you will fill in for "transit" and with your onward flight, and presumably a hotel where you'll spend the night. Have a hard copy print out of your onward flight, with your (and each passenger's) name. When you arrive at PEK, you will take these and your passport to Immigration. If the TWOV desk is open/staffed, go there. If not, go to the "Special/APEC" queue. If that is also not staffed (unlikely unless it's late at night), then go to any queue for Foreigners. They'll look at your stuff, stamp you in, and then you may proceed to Baggage Claim then through Customs (normally just a walk-through) and out to the exit and ground transportation.

If your layover is only for 24 hours, then that is what you will get, not the 72-hour extended layover.

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