Picturesque meant - he decided after careful observation of the scenerey that inspired Twoflower to use the word - that the landscape was horribly precipitous. Quaint, when used to describe the occasional village through which they passed, meant fever-ridden and tumbledown. Twoflower was a tourist, the first ever seen on the discworld. Tourist, Rincewind had decided, mean 'idiot'.
Terry Pratchett (2008). “The Colour Of Magic: (Discworld Novel 1)”, p.101, Random House