A great place to start the day if you are in South London is Federation Coffee in Brixton Village. The food is great and so is the coffee. This is a very chilled place where you can get both and indoor and outdoor experience (even though the whole place is under the Village roof).
Getting lost is an age old suggestion but a good one. Put away your cell phone or your A-Z and just wander around. I still do this regularly even though Ive lived here for nearly 10 years. London is a big city and it drip feeds you its secrets sometimes. You will come across things you wouldn't usually, in amongst the Starbucks and pret a mange there are some amazing sights. Just 'being' somewhere is a great experience and one no guide book can help you find.
Sager & Wilde is a small wine bar on Hackney Road, close to many other amazing places on Hackney and Columbia Road.
The perfect place for an aperitif or a nightcap.
I love the architecture of the Barbican - it is so important to its historical context, at a time when London was being shaped for modernity after the war - they also aspired to make it a bold art centre. We need bold, always.