Whether you can ride a bike thought the park will depend on whether or not there are cats and elephants in there. I don't know the answer I'm sorry.
Western Zambia is un-developed. If you are looking for that, then you will find it.
When you get to Lusaka you can decide. The local operators in Livingston may be your best bet to ask. And you can see how you are feeling about the whole thing.
The Kazungula/Kasane border can also cross to Zim and is only 50 minutes form Vic Falls that way. But there's a $50 visa to buy each etc for Zim. Zim is a beautiful country, still very safe to travel in. Fuel is the main problem. And the corruption.
But cross over the ferry and exit Zambia. The Border's fine. It's cheaper and easier, but not as nice. Livingston will be your first taste of 'real' Africa after the Caprivi.
All the roads form that part of the Caprivi are good. The roads from Zasane south to Nata and Martin's Drift are good, but hot and boring. Don't do them at night because of the wildlife. The police in Bots have radars, and often sit just inside the change to the town speed limit sign, when you are still doing the open road speed. And you have to pay on the spot, with or without a receipt.
There are 100 different routes and no 2 people want or will pick the same one.
If you are going J'Burg to J'Burg, then I am guessing that you are coming from South Africa and though Namibia into the Caprivi. Shooting back via Martin's Drift.
Another option is to do southern Zambia and South Luangwa Nat Park (more developed), (a relative term), able to camp on the edge of the park, with hippos and elephants coming into the camp, and take game drives into the park in 4wds.
From there you could return to Lusaka. Or, if you had the time, it's an easy hop to Malawi, south though Mozambique and on to J'Burg. There's always somewhere else to go and a different way to get there.
But as Jeff says, western Zambia will be the real Africa and you'll see precious little of it in South Africa, Namibia and Bots, so go for a look.
But I would think that you will be lucky to be allowed to ride a bike though any National Park and a brave man to do it. Being inside my 18 tonne truck I felt decidedly vulnerable sometimes.
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