The maximum length per segment of 100 meters has to do with attenuation, basically that is the limit you can push the electricity down the wire. I've done up to about 130 meters or so successfully at 100 mbs with good wire and fittings, but it is not wise to push the limit because hardware and channel are designed with specific parameters.
Now, the maximum length overall has to do with timing, as I understand it. Essentially it takes too long to get the packet to the other end, and get acknowledgement, so it may retry before it actually needs to causing collisions and little to no thru put.
The correct options include wireless, long haul modems, fiber, etc. It is not wise to put little switches in at each 100 meter segment and try to push it 500 meters or more. For the cost, fiber can be quite competitive in your specific situation.
Good Luck! It is only my opinion, based on my experience and education...I am always willing to learn, educate me!
Daron J. Wilson, RCDD
daron.wilson@lhmorris.com