To run Web inspector from Google chrome your BB10 device must be connected form the system (either by USB or wifi). In case of BB10 simulator, as vmware adapter is already connected to your system adapter so you need not to worry about ip address showed by BB10 browser's Web Inspector option.
To start Web Ispector of BB10 browser from Google chrome follow the 3 steps:
Select NAT as vmware network adapter setting (It should also work with Bridge connection but i have only tried with NAT).
On the Web Inspector in from the BB10 Browser.
Type IP address showing in the bottom left corner of the simulator followed by default port "1337" (i.e. 192.168.10.256:1337)in Google Chrome.
It will start working.