You can at any time send from any or all addresses you have funds into.
You can choose the sources using "spend from" (for addresses) or coin control (for specific inputs, so even more specific). I use r-click/spend from, from addresses tab, which I recommend you make visible so you'll understand better what you are doing.
Even more, I recommend you play a little with Electrum on Testnet (so with free dummy coins) so you can see for yourself much better and then come with more specific questions.
For example, if you have the option of five receiving addresses, it means you can send funds to these five addresses. Why would you need five different sending addresses while the five receiving addresses are acting as sending addresses too? I hope you understand my point now or not. If you want to send funds to another wallet that has five different receiving wallets, you have the option to use those five receipt (deposit) addresses to send funds, which means you have the option to choose from five sending addresses indirectly.
Under the tab named 'addresses' I see something like this many times over some with zero balances:
Type Address Label Balance Tx
receiving xxxxxxxxxxxxxxxxxxx .0008000 1
change xxxxxxxxxxxxxxxxxxx 0.000536 1
You can only use the 'Spend From' under the Addresses tab of Electrum if you have money in it's balance. Right click on mouse to get 'Spend From'.
I see many more addresses with nothing in them under the addresses tab in Electrum, these don't offer you the option 'Spend From' when you right click them with mouse, the only ones that did were had money in them.
I see some 2's under Tx, I am not sure what that means.
I am not sure what it means by 'Type change'.
I see that this is highlighted in green 'coin control active" and a reset button. How do I reverse what I just did?
To get more addresses to send from you would need to receive more first i.e. click the generate 'New Address' button then go to tab called Addresses and right click and scroll down to Spend From, select that, and now you have a new address to send btc to others. How much privacy does this give you?