Main difference for a package maintainer (I think that would be 'developer' in Debian lingo) is the way package meta-data and accompanying scripts come together.
In the RPM world, all your packages (the RPM's you maintain) are located in something like ~/rpmbuild. Underneath, there is the SPEC directory for you spec-files, a SOURCES directory for source tarballs, RPMS and SRPMS directories to put newly created RPMs and SRPMs into and some other things that are not relevant now.
Everything that has to do with how the RPM will be created, is in the spec-file: what patches will be applied, possible pre and post-scripts, meta-data, changelog, everything. All source tarballs and all patches of all your packages are in SOURCES.
Now, personally, I like the fact that everything goes into the spec-file, and that the spec-file is a separate entity from the source tarball, but I'm not overly enthusiastic about having all sources in SOURCES. Imho, SOURCES gets cluttered pretty quick and you tend to loose track of what is in there. However, opinions differ.
For RPM's it is important to use the exact same tarball as the one the upstream project releases, up to the timestamp. Generally, there are no exceptions to this rule. Debian packages also require the same tarball as upstream, though Debian policy requires some tarballs to be repackaged (thanks Umang).
Debian packages take a different approach. (Forgive any mistakes here: I am a lot less experienced with deb's that I am with RPM's.) Debian packages' development files are contained in a directory per package.
What I (think to) like about this approach is the fact that everything is contained in a single directory.
In the Debian world, it is a bit more accepted to carry patches in a package that are not (yet) upstream. In the RPM world (at least among the Red Hat derivates) this is frowned upon.
Also, Debian has a vast amount of scripts that are able to automate a huge portion of creating a package. For example, creating a - simple - package of a setuptool'ed Python program, is as simple as creating a couple of meta-data files and running debuild. That said, the spec-file for such package in RPM format would be pretty short and in the RPM world, too, there's a lot of stuff that is automated these days.