Short answer is yes.
There are a few quirks of each operating system which take a bit of getting used to, some of which will feel right after a week or two and some you’ll wonder why on earth they do things this way for ever more but overall the differences are fairly minor and you’ll make the transition just fine. Not knowing the new keyboard shortcuts will make things feel a little slow initially but again it’s nothing you won’t pick up after a few weeks. It’s good to know both operating systems.
For me the worst thing about the apple systems are the mice, I find the shape of the magic mouse to be the second most uncomfortable mouse i’ve ever used (the first was an earlier apple mouse), see how you get on with it but if you start to find it uncomfortable you might want to switch back to a less slick looking but more ergonomic mouse.
As for the phone and the music, depending on what else you have on the phone the 32GB should hold all your music at a decent bit rate. If you get given the 16GB model then I doubt you’ll have enough space. So i’d hold off buying the iPod and wait and see what capacity phone you get given first.
Good luck in your new job.