You don't actually post to someone's wall, rather you post to your own wall, specify which circles (groups of friends) can see this and it will appear on their wall.
So, if you post a picture and specify that your "friends" group can see it, it will appear on the walls of all the people in your "friends" group. You can of course post to multiple groups and can have people in multiple groups.
A good idea is to spend some time setting up your groups before you get stuck in to using it. And don't forget to send invites out to your friends.
You can comment on posts which you or your friends have posted.
I accidentally spammed a few people with emails with my first three posts...people were needless to say not interested in me rooting my Acer Iconia! ;-)
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