In general it is faster and less trouble to get your visas in Africa rather than in Europe before you go. It also tends to be easier to get visas when you don't have a vehicle of your own. It isn't normal for embassies to ask for letters of invitation or onward plane tickets if you simply let them know you are transiting through. If they do ask for hotel references then a quick phone call to any well known hotel in your destination country with an "assurance" that you will be staying there when you arrive is all you need, coupled with a letter which you can easy produce yourself. If the embassy wish to check your reference with a phone call (very unlikely) then you will be covered.
In general visas are not difficult to come by on the western route to Cape Town although being Africa things are constantly changing obviously. At present you can get Gabon, DRC and congo visas in Yaoundi very easily (24 hours each) and then get a double entry Angola visa in Libreville where passports need to go in on the Monday for collection on Friday. As a general rule visas are becoming easier to get rather than more difficult on this route so I don't think you have too much to worry about. Good luck!
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