OneLittleLady order samples online from Les Senteurs and Scent and Sensibility (or, if feeling very adventurous, from Surrender to Chance in the US). Both have a great selection of niche fragrances (unusual, "artistic" perfumes - often there is no going back after getting to know them) and I find them real treats. On the high street, Chanel and Hermes and Estee Lauder still do quality perfumes, and in bigger dept stores you can find niche lines such as Serge Lutens, Annick Goutal, Diptyque, Tom Ford and L'Artisan Parfumeur - many others can be very hit &miss.
A great guide to this new territory is the Turin&Sanchez perfume guide or the small book 'Le Snob - Perfumes' (mistitled, not snobbish).
I prefer 1ml of unique quality perfume (often frugally sourced from Crystal Flacon) to 100ml of schlock but that is a very personal preference 
A couple of budget operators - Yves Rocher, L'Occitane - are quite quality conscious and the Lidl juices are not bad (they do copies of Coco Mademoiselle, Chanel No. 5, Tresor and Boss) - but don't expect tremendous lasting power.
SOTD Eau du Sud - the opening is a burst of tart citrus, the drydown smells like a warm, summery meadow in Tuscany 