Well, if my experience is anything to go by, the switch will be pretty painless. The system sets itself up very quickly and smoothly and then you are up and running. As usual, I tend to set up an Admin account (with administration privileges) and User accounts (with just normal privileges) even if it is just me using the computer. I have automatic log-in set to off sand et the log-in display to show name and password fields.
Additional 'system' software I use is Intego security software (
Mac Anti-Virus & Security - Intego), Onyx (
Onyx Mac – Instant Download Onyx for Mac OS X) for the odd bit of maintenance (useful if you do not run the machine continuously as you can force maintenance scripts etc to run), AppDelete (
AppDelete by Reggie Ashworth) and VNC for remote access (
RealVNC - Download VNC® software). My guess is that for a new and expensive laptop it might also be worth checking out the tracking software in case it is stolen - it is reputed to work very well in aiding recovery. I also use VMWare Fusion to run a PC virtual machine for some things but I doubt you will need to.
System functions like log-off, shutdown and restart are accessed by clicking on the Apple symbol at the top left of the screen. System settings are all housed in system preferences (same button or gear wheel symbol in the icons at the bottom of the screen - the Dock). Adding printers etc can be done via that route and is usually as simple as clicking the + button and letting the Mac find the printer and set it up. You do not need to be logged in as an administrator for this as the system will ask for the admin password etc at the appropriate point.
Other software: For image editing I tend to use LR, PS and Nik and occasionally the tools from Pixel Genius. I also use CaptureOne and MediaPro from PhaseOne - the former to convert the raw files from PhaseOne backs to TIFF files which I then import into LR. Although I have a number of LR catalogues and one Master Catalogue, the entire image library is indexed using MediaPro as that's what is was designed for. For Video it is Premiere Pro and After Effects (which are part of the Master Collection). You should not need any extra Codecs and the like but the learning curve is pretty steep. I have been meaning to try Final Cut Pro X. I know it has not been popular with seasoned professionals but for more modest projects it could be perfect especially as I record directly into ProRes (which Premiere handles also).
As was mentioned elsewhere I would also look at getting an Intuous tablet at some point. The smaller A5 wide style are perfect for photo editing; the larger ones are just tiring to use and not well suited - they are more for graphic artists working on larger 'canvases'. But you need some sort of mouse as well. The Apple Trackpad is very nice but, even so, a mouse is useful. I developed a spot of RSI and it got to a point where I would get pains near my elbow that would occasionally wake me at night (and I do not consider myself to be a heavy user of the mouse and prefer keyboard shortcuts). I tried various ergonomic devices and the only one that worked for me was the Evoluent Vertical Mouse (
Evoluent VerticalMouse, Vertical Mouse, ergonomic mouse, ergonomic computer mouse, computer mouse, optical mouse, carpal tunnel syndrome, repetitive stress disorder, RSI - I prefer the 3 to the 4). Within a couple of weeks the pain had gone and has not returned. If that is not a problem then the Magic Mouse is indeed a thing of wonder! It works as a mouse with the usual functionality but its surface also functions as a track-pad.
I keep my monitors calibrated using the iOne Photo spectrometers and find my laptops to be amazingly accurate. On the MacPro in Germany I run 3 monitors, all NEC, and one is a SpectraView - all are calibrated. I use a top spec Mac Mini for editing at IMSL in the UK and that is fitted with an Eizo Color-Edge monitor.
Not sure what else to add. I'm pretty sure it will be a fairly painless transition and I'll be interested to see how you get on with Mountain Lion. I did not migrate from Snow Leopard although the newest Mac Mini came with Lion installed (the one in Germany is a server).