You can't switch endianes for testing purposes or anything like that. What you can do is, to install an emulator for a big-endian architecture and compile your program for the emulator. Here's one way, under:
http://people.debian.org/~aurel32/qemu/
are Debian disk images for all kinds of QEMU supported architectures. mips, sparc and arm are big-endian (do not download anything ending with -el). I'm using Debian Lenny for MIPS ( http://people.debian.org/~aurel32/qemu/mips/ ). Install QEMU for your platform, then follow the instructions on the MIPS-page to download a image and kernel file.
Now you can boot into a Debian 5 for MIPS right from your console. Login to you virtual machine, become super user (the password is "root") and install the C-compiler:
debian-mips:~# su -
debian-mips:~# apt-get update
debian-mips:~# apt-get install gcc
fire up an editor and enter your program:
debian-mips:~# pico foo.c
debian-mips:~# gcc foo.c
debian-mips:~# ./a.out
big endian
UPDATE (2021-07-27) Just want to add, for anyone reading this 11 years later, that using the multiarch privileged container in docker is an easier and faster way to get a testing setup. Getting a s390x (big endian) running is as easy as:
$ docker run --rm --privileged multiarch/qemu-user-static --reset -p yes
$ docker run --rm -it s390x/ubuntu bash
Also, this works unter Docker Desktop for Windows.
See https://github.com/multiarch/qemu-user-static for more infos.