A straight forward way is to use Migration Assistant: http://support.apple.com/kb/HT4889
You can also connect the two Macs with an ethernet wire (regular one, not the crossover type) and just drag files from the old to the new.
You can also start up the old Mac in Target Disk Mode and the hard drive will appear on the new Mac's desktop and you can drag files out and to the new Mac.
All of this holds true for all content on the old Mac, including Word, Excel, etc. files.
Have a look at > Switch Basics: Migrate your Windows files or system to your Mac
Depending on your PC you might be able to use Migration Assistant, although Manually migrating using an External HD is probably the fastest and safest way.