Cold booting a 68k Mac straight into an alien OS is a bit difficult. It's not undoable, but there is a lot of hardware out there which needs to be set up before use (much like most VGA cards, which have a ROM with x86 code used to set the card up, making their use on non-PCs next to impossible), but once MacOS has done its job, nothing prevents you from using a second OS loader to throw MacOS out.
NetBSD has been ported to the Mac since ages, and it uses this approach (though a bootloader not involving MacOS at all has also been investigated). And since it's BSD, it's free for your use.
Another path is that one used by MagiC, a reimplementation of Atari's TOS. While it's originally for the real Ataris, it's been ported to the Mac, but runs inside MacOS, on its own screen. This makes porting much simpler, since you're addressing MacOS interfaces, instead of the hardware devices themselves. Much like Shapeshifter et al on the Amiga. I've always wondered why no-one just ripped the CPU emulation out of UAE and compiled it for the Mac. After all, there is already a MacUAE, just not for the 68k ones.
(On another note, the only way to play MP3s on a 68k Mac is by running an Atari MP3 player under MagiC; Mac users themselves have always claimed that a 68k processor can't handle the load. ;-)