At the end of the day, everything is an API.
Need to write code for an SPI peripheral inside a microcontroller? Well, get the datasheet or hardware manual, and look at the SPI peripheral. It's one, big, complex API.
The problem is that you have to understand the hardware and some basic EE fundamentals in order to comprehend what the API means. The datasheet isn't written by and for SW developers, it was written for hardware engineers, and maybe software engineers.
So it's all from the perspective of the hardware (face it - the microcontroller company is a hardware company filled with hardware/asic engineers).
Which means the transition is by no means simple and straightforward.
But it's not difficult - it's just a slightly different domain. If you can implement a study program, start off with Rabbit Semiconductor's kits. There's enough software there so a SW guy can really dig in with little effort, and the HW is easy to deal with because everything is wrapped in nice little libraries. When they want to do something complex they can dig into the direct hardware access and fiddle at the lower level, but at the same time they can do some pretty cool things such as build little webservers or pan/tilt network cameras. There are other companies with similar offerings, but Rabbit is really focused on making hardware easy for software engineers.
Alternately, get them into the Android platform. It looks like a unix system to them, until they want to do something interesting, and then they'll have the desire to attack that little issue and they'll learn about the hardware.
If you really want to jump in the deep end, go with an arduino kit - cheap, free compilers and libraries, pretty easy to start off with, but you have to hook wires up to do something interesting, which might be too big of a hurdle for a reluctant software engineer. But a little help and a few nudges in the right direction and they will be absolutely thrilled to have a little LED display that wibbles* like the nightrider lights...
-Adam
*Yes, that's a technical engineering term.