In OE there are 2 way to do this.
Create two new folders. Call one Personal and the other Business. In the Tools menu, set up two new Message Rules for Mail. The first rule should be set to move any incoming mail to your business address to yourBusiness folder from the inbox on receipt and the second to move personal mail to your Personal folder.
eg Mail Rule 1. Where the To line contains people....move to Business. The To should be set to your business email address. eg info@mybusiness.com
Mail Rule 2. Where the To line contains people....move to Personal. The To should be set to your personal email address, eg
me@homeemail.com
You will then need to set two Mail Accounts, one for business and one for home. Give them obvious'friendly names' e.g. Home Mail and Work Mail. When you write an email, you have to use Send Using.....and then it prompts you to choose which email account the message is sent from.
You may want to create separate Sent mail Folders eg Work Sent,Home Sent and apply message rules to your outbound mail too, instead of storing it all in the sent mail folder.
The second method is to set up two 'Identities' Call one 'Work' and the other 'Home'. Enter the details for each Identity and then youwill have to 'log-in' to OE to use the two identities.