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Originally, the letters showed the order, just as the chapters in (say) the Iliad: Alpha indicated "chapter one", Beta was "chapter two" and so forth. That was fine for the first 24 chapters, but when Omega had been assigned to the (short-lived) Naval Academy chapter, the chapters decided to double the letters, so Monmouth was Alpha Alpha, Iowa was Beta Beta, and so forth... I seem to recall there was an interesting situation about Zeta Zeta which I hope our ZZ-kai- brother will explain... then (in the great year 1872!) they revised the scheme again, and changed all the two-letter names so that the first letter was Alpha (thus Iowa became Alpha Beta).
Then there was the "low-name-hunt" - I think Hanna (or was it Chandler) tells about this... and chapters tried to get the names of defunct chapters, which is how there was some shuffling, and how Stevens got Sigma and Penn got Phi and the re-chartered Davidson had to accept "Phi Alpha" (the "first" Phi)... lots of intricate history to tell here, but I don't have the books nearby. There were also a handful of chapters where they were permitted to use some local designation, such as Mu Epsilon at Wesleyan and Zeta Phi at Missouri and Tau Sigma at Iowa State... the rules were changed again, and strict order has been maintained, except there have been one or two odd cases even recently - upon my recommendation the General Secretary proposed and the convention ratified Priceton to be given an out-of-order name (Theta Epsilon) to suggest her ancient identity.
As I recall, much of this is detailed in Shep's Beta Book, which you should consult for the correct information - as the years have run on since J Cal and George M. and Shep and I used to hang out and talk about Greek...
"In days of yore on a Greecian shore..."
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