Open a Finder window. From the menu bar click Go > Go to Folder
Type or copy / paste the following:
Click Go then move the Cache.db file to the Trash.
Quit and relaunch Safari to test.
BTW, if you enable the Develop menu you can empty the Safari cache easily instead of having to go through your user library.
From the Safari menu bar click Safari > Preferences then select the Advanced tab.
Select: Show Develop menu in menu bar
Then from the Safari menu bar top of your screen, click Develop > Empty Caches
Upgraded to OS X Mavericks 10.9.4 two days ago, and with that inherited a problem with the "Reopen All Windows from Last Session" feature. Before the upgrade, Safari would ask if I was sure to quit N amount of windows when quitting, and during next session would allow me to "reopen all windows from last session". In the new version of Safari (7.0.5) this option does not work.
Tried emptying caches and plug-ins as mentioned in other threads with similar problem, but the problem persists. Thanks for getting back on this!