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Hi there,
I think it would be a pity to make the trip by plane, since there are some very good national parks along the way from Zambia to Namibia. You should try to find an overland tour operator or a bus company that makes this trip. For company names or addresses I dont know, but surely you can find a good selection online.
Along the way you should at least try to see Chobe national park and the Okavango delta - two really amazing places for scenery and wildlife.
If you wanna try Zimbabwe even thou its a little out of the way, Hwange National park is also a good spot.
Finally in Namibia, swing by Etosha national park, a must see.
I did all of the above mentioned last year on an overland tour with a local company called Drifters.

If you budget is not too tight, a helicopter ride over the Victoria falls is amazing and well worth the money (about US$125) for 18 minutes of flight

For travelling alone as a female Im not really the one to give advice (Im a guy), but generally the population is friendly and curious, rather than dangerous in my opinion.

Good luck!

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Chobe national park and the Okavango delta - a must visit two really amazing places for scenery and wildlife day trips or overnight stays can be arranged depending if you book in one of the fancy resort hotels they will organise everything. l am also travelling to Livingstone Zambia to see the falls and Chobe for a day trip, my dates are the week beginning the 18th of Feb 2013 and am goin for a week.