From the pbdedit man page:
The pdbedit tool uses the passdb modular interface and is independent from the kind of users database used (currently there are smbpasswd, ldap, nis+ and tdb based and more can be added without changing the tool).
While the smbpasswd man page:
By default (when run with no arguments) it will attempt to change the current user's SMB password on the local machine. This is similar to the way the passwd(1) program works. smbpasswd differs from how the passwd program works however in that it is not setuid root but works in a client-server mode and communicates with a locally running smbd(8). As a consequence in order for this to succeed the smbd daemon must be running on the local machine. On a UNIX machine the encrypted SMB passwords are usually stored in the smbpasswd(5) file.
pbdedit can manipulate a variety of Samba password backends, while
smbpasswd can only manipulate that type of backend.