I think that it depends on the way that they program in their chosen environment, and the type of embedded work that you're talking about.
Working on an embedded linux platform, say, is a far smaller jump than trying to write code on an 8 bit platform with no operating system at all.
If they are the type of person that has an understanding of what is going on underneath the api and environment that they are used to, then it won't be too much of a stretch to move into embedded development.
However, if their world view stops at the high level api that they've been using, and they have no concept of anything beneath that, they are going to have a really hard time.
As a (very) general statement if they are comfortable working on multithreaded applications they will probably be ok, as that shares some of the same issues of data volatility that you have when working on embedded projects.
With all of that said, I've seen more embedded programmers successfully working in PC development than I have the reverse. (of course I might not have seen a fair cross section)
