I don't think there is a thread specific on painting pleather shoes and there is contradictory information on if it's possible or how to do it on the many threads touching the subject so I though I'd share my experience with it:
What paint I used
After doing a lot of research I found that the paint most people agreed on was Liquitex Acrylic Soft Body. However, my local art supplies store only carried Heavy Body. The difference between the two is that Heavy is thicker and applies more in a sculpted way. To thin Heavy Body into Soft Body I mixed it with Liquitex Fluid Medium Matte. (You can use the non-matte version depending on the look you're going for).
Paint/Fluid Medium ratio
I think after all this was a better solution than using Soft Body as I could control the thickness of the paint and used various thickness depending on where I applied it.
At first, I used about 60% paint/40% medium but since I was painting black pleather into bright gold I thickened it after the first few layers to about 70%~80% paint. It covered well but you could see the paint strokes sometimes so I finished it off with a thinned out layer of paint.
I used masking tape to protect the part of the shoes I did not want painted.
Applying the paint can be really tricky since it can be pretty thick so you have to smooth it with the brush in every direction for a long time. The paint also dries pretty fast, which is a blessing as you will need to apply MANY layers of paint. I think I must have painted at least 10 layers.
The first few layers with thinner paint: http://www.cosplay.com/photo/2713936/
After a full afternoon of painting/letting dry/painting/etc. : http://www.cosplay.com/photo/2713937/
Con + painted shoes
I spend the whole con in the shoes, I crouched, jogged, walked on pavement, on gravel, grass, etc. and I was really impressed by how well they the paint held. By the end of the con it had only peeled off a little in one spot and had cracked in the creases a bit but you can't really tell unless you're looking at them up close. I could have covered them every evening with the paint and they would've been dry for the next morning but I was lazy. :P
Both shoes: http://www.cosplay.com/photo/2713938/
Cracked paint in the creases: http://www.cosplay.com/photo/2713939/
Small part that peeled off: http://www.cosplay.com/photo/2713940/
I'm currently in the process of fixing the damage: http://www.cosplay.com/photo/2713954/
First picture: 1 layer of paint
Second: 2~3 layers
Third: ~5 layers.