UPDATED. After Peter May and Kate Ponto released their new book, there are very readable introductions to many of the topics on the "second level" of algebraic topology.
There is a wonderful book on Cohomology Operations by Mosher and Tangora. It is thin (and only discusses one topic), but very nice.
May & Ponto's new book is very nice. It covers three topics (Professor May's comment above has details) + an appendix on spectral sequences, which is short but very much to the point. I used to fear that any book by May was secretly about category theory, but that is not true about 3/4 of this one (unless the secret is hidden too well).
There is a pretty good, and comprehensive book by Fomenko and Fuks (or Fuchs?) on homotopy theory. I've only seen the Russian version (so I can't vouch for the translation). It's also not very well-known, and not very easy to find, which is a shame (the Russian version is more obtainable). It has a lot of stuff, including one of the nicer introductions to spectral sequences (although I don't know a single book that does this well. Serre's thesis is nice, Hatcher's notes are OK, but this seems to be a topic best learned in a good class). It's also very readable. Here's a reviewreview (institutional access probably required) with a description of its contents.