Using SVN technically, won't be an issue - especially with Tortoise +VisualSVN (latter not free but cheap).
The headspace change in going from the usual VSS way of working - pessimistic locking - to the SVN/rest of the world style - optimistic locking will be the harder hurdle.
To explain a little less concisely - if you are used to locking a file when you 'check it out' so noone else can change it, or at least everybody else knowing you are working on it before they try to make any modifications it is quite a leap to go over to not knowing until you try to commit - at which point you have to do merges.
Merging is the tricky bit sometimes, purely conceptually, but especially merges for Winforms with the designer auto-code and the resx files...
Think very carefully about your branching strategy. Best to start just working directly off of trunk to get used to the software before deciding to go for merging. You will find a lot of things quite repetitive and manual compared to VSS - we have a coupla guys here who admin the SVN servers and thay have been invaluable in writing scripts and add-ons for Tortoise to take some of the pain away...