A lot of people have never read the Bond novels and the success of Skyfall have gotten people interested in the books, here is some advice:
1. Read them in order of publication, including the short-stories. Start with Casino Royale and end with Octopussy and The Living Daylights. This will help in the later novels.
2. Clear your mind of the movies. There are no space based weapon systems, no volcano lairs, no lasers, no space flights, no Bibi Dahl.
3. Understand the era. Bond was born around 1920, most of the Bond women in the novels were born in the around 1930. There are things like 'wire recorders' in the novels that people will not have any idea what they were. If you need to, look them up on the internet. The kindle versions will help since you can get a definition.
4. Read them slowly including the "boring parts". Fleming paints a picture. He does not come out and says "the man dropped a grenade in the water", he will describe the action instead. Also, there are many references to gothic literature and mythology in the novels, if you read the books too fast you will miss them. The books were written in a time when people read and did not watch TV.
5. Ignore the continuity mistakes from novel to novel; Fleming was unaware that his novels would be successful and he never wrote fully anticipating he might have to be consistent in future editions.