It's all about when you have very long runs of cables (20ft+) you can suffer a loss of highs (only affects passive pups as they're high impedance). In those cases a buffer will most likely help.
A lot of pedals are essentially buffered when they're on, yep. Also if you've got any pedals that aren't true bypass, they're buffered when they're off too. How the buffer is done will determine how much effect it has on your signal. The Klon buffer for example, is very transparent. Boss, not so much.
The only other thing to note is that buffers will screw with some old fuzzes and wahs, so will need to go after them in the chain.
If you're handy with a soldering iron, you can make yourself one for peanuts, there's not much to them:

Thinking about it, I could knock that together in a 1590A for about £20 delivered and make it look pretty cool.