On Windows, both / and \ function as pathname component separators (dividing the name of a directory from the name of something within the directory). On basically all other operating systems in common use today, only / serves this function.1
By taking \ literally in header-file names, instead of an escape character as it is in normal strings, GCC's preprocessor accommodates Windows-specific code written with backslashes, e.g.
#include <sys\types.h>
where it is exceedingly unlikely that the programmer intended to include a file whose name is 'sys ypes.h
' (that blank before the 'y' is a hard tab). The text in the manual is intended to inform you that such code will not work if moved to a Unixy system, but that if you write it with a forward slash instead, it will work on Windows.
I happen to have written the paragraph you quote, but that was more than ten years ago now, and I don't remember why I didn't use the word "Windows".
1 VMS and some IBM mainframe OSes have entirely different pathname syntax, but these have never been well-supported by GCC, and it is my understanding that surviving installations tend to have a POSIX compatibility layer installed anyway.