Your save games should be under c:\users\your_login_here\saved games(somtimes it is documents\saved games, but it will only be in one place).
If you are worried about save games, take a backup of that folder.
Now you seem to be wanting to shrink drives and stuff. This is all good, but the upgrade to Windows 7-64bit part has be wondering. What is your current OS.
If you are a Steam user(Steam should be closed while moving games this way.) your game should be under C:\Program Files (x86)\Steam\steamapps\common\Skyrim\
In that case, you could copy the game over to your G drive lets say g : \ games \ skyrim
then rename the Skyrim folder in the steam folder to skyrim 1 if you are worried(but you already should have a copy in g drive).
Then you can either make a Skyrim folder to just the software mentioned above OR use the command prompt.
OR
not make a skyrim folder and use the command prompt. Hitting enter after each line.
Code:
cd\
cd Program Files (x86)\Steam\steamapps\common\Skyrim
mklink /J "Skyrim" "g:\games\skyrim"
That would create a Junction called Skyrim in the Program Files (x86)\Steam\steamapps\common\ folder
With Steam you also have a 3rd way to do this trick. I tried this to see if it would work.
1. Open Steam
2. Select View then Settings
3. Select Downloads
4. Select Steam Library Folders
5. Add a folder on your g drive(ie g : \ games \ steam).
6. Close that window and close Steam
7. Check that new folder to see if you now have a SteamApps folder in this new library(g : \ games \ steam).
8. Go Cut Skyrim from your normal Program Files (x86)\Steam\steamapps\common\Skyrim location and paste it into your new steamapps folder (it should be something like g : \ games \ steam \ steamapps \ common \)
9. Go get your skyrim ACF file from your old normal steam folder (Program Files (x86)\Steam\steamapps\) and copy it to your new folders steamapps folder
This file will be called appmanifest_#####.acf. Skyrim uses a different appid depending on what version you own.
72850 = The Elder Scrolls V: Skyrim
28187 = The Elder Scrolls V: Skyrim - Legendary Edition
You my have another(I am sure they have had many different app-ids), check on SteamDB or even Google to see what your app ids are.
10. Load steam and login. Try to run the game, if it gives you no errors, your game is not in your other steam library without any fancy junctions or symbolic links.
If you have any questions, let me know.