Context Path of portal can be changed by following the steps(eg. root-->portal):
1. Add portal.ctx=/portal to portal-ext.properties file(create a new if it does not exist by you yet).
2. Rename the "ROOT" webapp folder to "portal".
3. Locate the context configuration file "ROOT.xml" under <installation-path-of-your-apache-tomcat>\conf\Catalina\localhost and rename it to "portal.xml",then correct the path attribute to "/portal".
4.Start the server and we can access Liferay by www.liferay.com/portal.
Questions related to two instances:
It seems that it's impossible for two instances to have two different Context Paths in one portal. If not , how can we achieve it?
Backup about how to run a new instance(e.g www.vcvijayan.com):
1.Login as admin and navigate to Control Panel→ Portal Instances,add a new instance and save it
2.To get the virtual host work we need to add it in hosts file.Navigate to C: → Windows → System32 → Drives → etc → hosts file
3.Append the following line:127.0.0.1 www.vcvijayan.com
4.Restart the server and access the URL in brower: www.vcvijayan.com:8080,done.
Questions about accessing the new instance from different URL:
What's the essential difference here between accessing the URL www.127.0.0.1:8080 and www.vcvijayan.com:8080 ?

