Is it a simple as OpenType is better than TrueType is better than PostScript?
All depends on your usage. If you deal with prepress or press shops a lot, then you definitely want to use PostScript fonts. Professional RIPs don't like TrueType fonts much. Otherwise, TrueType is fine for general use. OpenType fonts have a great advantage in style choices. Older 8 bit fonts (TrueType or PostScript Type 1) are limited to 256 glyphs (characters). OpenType can handle 65,000 glyphs per type face (actual count is 65,536, which is 256 squared). You'll find tons of special swash characters, ligatures and other stuff to play with if you're really into typography.
OpenType isn't really any "better" than TrueType because OpenType fonts can be purchased in either TrueType or PostScript format. Though since PostScript fonts are handled just fine in OS X for printing and cost no more than TrueType versions, I'd suggest always purchasing the PostScript version when you have the option. Here's a short rundown on common fonts and their file suffixes.
Usually no file suffixes - Type 1 PostScript, 256 characters. Separate screen and printer fonts that must be kept together in the same folder to work.
.ttf - original TrueType Font, 256 characters.
.ttf - TrueType Family, 256 characters. More than one type face bundled into what looks like a single font.
.ttf - OpenType TrueType font. 65,000 characters. And no, it's not a mistake. They really did give all three TrueType versions the same file suffix.
.otf - OpenType PostScript font. 65,000 characters.