Anyone interested in tackling Ulysses in 2014 would benefit greatly from Frank Delaney's ongoing Re:Joyce podcast, in which he "unpacks" the book a paragraph or so at a time. He's been at it for three and a half years and is almost through "Calypso", the fourth chapter. That's an advantage for a first-time reader, as it gets you through the (deliberately ponderous and self-indulgent) "Proteus" stretch in Book I.
http://blog.frankdelaney.com/re-joyce/
Ulysses is a singular book: Well-worth it if you love language, or for that matter almost anything about life as it is lived.