Red, Green, and Blue match up as you'd expect to the breakout cable's connector. Black goes to all those wires that are crimped together into the break cable connector.
White is for composite sync. A lot of people just twist together the separate VSYNC and HSYNC signals like you say, and it often works, but it also runs a small risk of breaking your video card, and it may not work. To be proper, you're supposed to XOR them together with a logic gate like a 74LS86. Certain resistor combinations can also be used with varying degrees of success. You may also be able to set your PC to output composite sync via the drivers. If so, it's usually placed on the HSYNC line, leaving the vsync line unused and not connected.