I personally would recommend exploring the Frederic Malle and Serge Lutens fragrances lines, and perhaps some from the Comme des Garcons, L'Artisan, and Tom Ford Private Blend line. These are some of the most talked about on Basenotes, though there are literally thousands of niche perfumeries out there; the selection is endless.
As for which particular fragrances to try, read some of the descriptions and reviews in the directory and see what appeals to you. There really is no right answer, just forum favorites and so forth; it all depends on what you enjoy in a fragrance.
Have fun exploring!