Grain is not a natural medium for growing mushrooms. It is a rich source of nutrients, which bacteria, mold and yeast are much better at quickly exploiting than the edible fungi. When we use grain as a starter, it is typically sterilized in a pressure cooker for 90 minutes at 15 psi to kill all the competing organisms, then it is inoculated in a sterile environment with the desired fungi.
Many different grains are used for mushroom spawn, but my favorite is rye, because it is the easiest to properly hydrate. If you get too little or too much
water in the grain, the mycelium will not grow properly.
I've never tried using bread as a starter, but I imagine the biggest obstacle is the texture - it seems to me that the bread would become a big gloppy mess if one moistened it and pressure cooked it. It might be worth trying several different "recipes" to see if a proper water to bread ratio is achievable.
I use wheat bran as a nutritional supplement (along with gypsum) for the sawdust fruiting blocks that are sterilized for two hours at 15 psi. I see no reason that bread could not be substituted for wheat bran in these blocks.
I've heard that a good use for old bread is as an ingredient in new bread (but I've never tried it.)