I have found a better way to do this than creating multiple partitions or using GRUB4DOS. All the files and folders for WinPE are the same.
1. Make a successful USB drive with your first WinPE build.
2. Rename the boot.wim in the sources folder of what you want to add (example: boot14.wim) with no spaces in the name and copy it to the "sources" folder of your USB drive.
3. Open up an Administrative command prompt in the "boot" folder of your USB drive.
4. Run the following command. It will give you the details of the of old entry in the boot loader. You need to note the GUID. In every case the default GUID is {7619dcc8-fafe-11d9-b411-000476eba25f}.
5. Copy the default boot entry to a new entry in the bcd store, that has to be updated.
Code: Select allbcdedit /store bcd /copy {default} /d "<Name of your WinPE build here>"
Note: Replace <Name of your WinPE build here> with whatever description you want to use and each entry should be unique.
6. The command in the previous step should have given you a new GUID; make a note of it.
7. Run the following commands. Replace boot14.wim with whatever name you used when renaming your WIM file.
Code: Select allbcdedit /store bcd /set {newguid} DEVICE ramdisk=[boot]\sources\boot14.wim,{oldguid}
bcdedit /store bcd /set {newguid} OSDEVICE ramdisk=[boot]\sources\boot14.wim,{oldguid}
8. Run the following command to see if the bcd store has the new ramdisk entry you created.
9. If you want to add more, repeat steps 2 through 8.
Credit goes to the person that came up with the tutorial originally. I just modified it a little. Here is a link to the original tutorial; it says it is for a Multi-Boot DVD but it could also be used for a Multi-Boot USB.
Multiboot