The examples in the wiki article show the difference pretty well. XPM lets you sort-of see what the image is just by looking at the source file.
E.G. compare this
static char blarg_bits[] = {
0x13, 0x00, 0x15, 0x00, 0x93, 0xcd, 0x55, 0xa5, 0x93, 0xc5, 0x00, 0x80,
0x00, 0x60 };
with this static char * blarg_xpm[] = {
"16 7 2 1",
"* c #000000",
". c #ffffff",
"**..*...........",
"*.*.*...........",
"**..*..**.**..**",
"*.*.*.*.*.*..*.*",
"**..*..**.*...**",
"...............*",
".............**."
};