The Price Editor, also called the price database editor, allows you to enter or modify prices for both investments and exchange rates between currencies. You can pull it up using the → menu item.

The first column in the dialog is labelled Commodity, which displays both trading symbols of securities and the symbols of currencies. In KMyMoney, a “Price” is the price of security in terms of a currency, or of a currency in terms of a second currency. For example, as I write this, the price of 1 USD in terms of 1 EUR is 0.94; that is, 1 USD costs 0.94 EUR. The first currency is the one being bought or sold, and the second one is the currency used to buy or sell it.
To manually enter a new exchange rate, press the button, and you get the New Price Entry dialog.

Enter the first currency (USD in the example above) in the Security field. Enter the second currency (EUR in the example above) in the Currency field. Enter the effective date of the price in the Date field.
Press the OK button, and you will then see the Exchange Rate/Price Editor dialog.

You can specify a price in two ways. You can enter the To amount or total price of the first currency in terms of the second, or you can enter the actual Exchange rate. In this case, since you are entering the number of EUR for 1 USD, those two values are the same. However, this is the same dialog used to enter an exchange rate when you enter a transaction which involves two currencies. In that case, you will generally enter the amount, and let KMyMoney calculate the exchange rate, taking care of any rounding.
KMyMoney can fetch currency conversion rates from the web. Once you have entered a single price for a pair of currencies, the online quote feature will always list that pair amongst its options.
See the section on Online Price Quotes in the Investments chapter for more details.