For the first ionization energy the outermost electron is removed. This requires the least energy because this electron is farthest away from the positively charged nucleus. After this electron is removed, the rest of the electrons are pulled in closer to the plus charged ion making it even harder to remove the second electron (which probably would have been harder to remove anyways because in most cases it would already be closer to the nucleus than the first electron was to start with).
If you look at IE's closely you can begin to understand why certain ions like sodium tend to form their normal values such as sodium forming Na+ and not Na2+ under "normal" chemical situations. You are told it is for "octet stability", but it is really because the second ionization energy for sodium is much much higher than the first.