Cab is easy enough from LUN into town. Hotel can arrange if you don't feel like haggling after an overnight. Neither option is expensive and the Holiday Inn shuttle was free.

There was a local airline running flights from LUN to Vic Falls. It's certainly do-able by bus (around 4 hours iirc) but if you aren't used to independent travel you might find the whole bus station at 6am with people milling around a bit off putting.

The falls is worth a good day. I left the bungee jumping well alone but thoroughly enjoyed a helicopter trip over the falls. Going over to the Zim side will be interesting if rather sobering. You'll need to pay for a visa...and make sure you get a double entry Zambian visa too. Also look at fitting a few days safari in. South Luangwa is world class but I really enjoyed Zambezi River. Canoeing was great fun (apart from being charged by a hippo ), so were the drives and walks. Cleared 4 of the big 5 in less than a day including a stunning male leopard on the hunt at night.

Zambia was my first trip to Southern Africa. It is a total travel cliche but I really do remember this beautiful soft light at sunrise and sunset, the trees, the landscape..... Just remembering reminds me why I travel.